CN1579934A - Columnar mesoporous silicon dioxide and its preparing method - Google Patents
Columnar mesoporous silicon dioxide and its preparing method Download PDFInfo
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- CN1579934A CN1579934A CN 03153264 CN03153264A CN1579934A CN 1579934 A CN1579934 A CN 1579934A CN 03153264 CN03153264 CN 03153264 CN 03153264 A CN03153264 A CN 03153264A CN 1579934 A CN1579934 A CN 1579934A
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Abstract
The invention belongs to the field of semiconductor material's preparation and application technology, especially columnar silicon dioxide. Utilizing basic ion surfactant as template and silicate ester as silicon source, hydrolytic condensation is done under alkalinity condition. The slenderness ration of columnar silicon dioxide is 2:1 to 1:1, length 600-200nm, diameter 300-100nm, specific area 800-1200m2/g and aperture 2.0-3.5nm. The invention has not only low energy consumption and a good dispersity, but also the slenderness ration can be controlled by changing reaction condition.
Description
Technical field
The invention belongs to the preparation and the applied technical field of semiconductor material, particularly relate to column mesoporous silicon-dioxide and preparation method thereof.
Background technology
Mesoporous silicon oxide is the noticeable research object in nanometer material science field in recent years.Hole in the mesoporous silicon oxide is to interconnect and contact with surrounding environment, and the quantity in its hole can be up to 10
19Individual/g, specific surface area is generally at 1000m
2About/g, high even reach 1200m
2/ g is so surface effects is very remarkable.Because the MCM-41 mesoporous silicon oxide has the three-dimensional open-framework of hexagonal symmetry, uniform pore size distribution, and because it has huge specific surface area and uniform hole dimension, make it important use be arranged, as the selectivity absorption of chromatogram, support of the catalyst, molecule, screening, catalysis etc. in catalysis and separation science.Mesoporous size make bigger molecule of processing or gene be called 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.[Robert I.Nooney such as Agnes E.Ostafin, DhanasekaranThirunavukkarasu, Yimei Chen, Robert Josephs, and Agnes E.stafin, Chem.Mater.2002,14 (11), 4721-4728] under alkaline condition, adopt cats product cetyl trimethylammonium bromide and neutral surface active agent's lauryl amine in dilute solution, to obtain the mesoporous silica spheres of 65～740nm scope by change silicate and surfactant concentrations.But because its reaction is to carry out in dilute solution, the very low and mesoporous silicon oxide that obtain of the productive rate of mesoporous silicon oxide is a spheroidal particle.
Summary of the invention
One of purpose of the present invention provides column mesoporous silicon-dioxide, and making its length-to-diameter ratio is 3: 1～1: 1, and column length is 600～200nm, and column diameter is 300～100nm, and specific surface area is 800～1200m
2/ g, the mesoporous 2.0～5.0nm that is of a size of.
Another object of the present invention provides a kind of method of synthetic column mesoporous silicon-dioxide simple to operate, easy to prepare.Present method can be carried out under higher concentration equally, and then reduces production costs, and the pattern of the mesoporous silicon oxide that makes is a column.
It is template that column mesoporous silicon-dioxide of the present invention adopts cats product, with TEOS is the silicon source, under alkaline condition, prepare mesoporous silicon oxide, the mesoporous silicon oxide that obtains is the MCM-41 mesoporous silicon oxide, and be cylindrical particle, and the length-to-diameter ratio of column mesoporous silicon-dioxide can be by changing reaction conditions, and control concentration of reactants, different solvent ratio, the power of alkalescence are controlled.
The length-to-diameter ratio of column mesoporous silicon-dioxide of the present invention is 3: 1～1: 1, and column length is 600～200nm, and column diameter is 300～100nm, and specific surface area is 800～1200m
2/ g, the mesoporous 2.0～5.0nm that is of a size of.
Column mesoporous silicon-dioxide of the present invention is to utilize cats product to be template, is the silicon source with silicon ester, and hydrolytic condensation forms under alkaline condition.
The step of concrete grammar comprises:
(1). the alcohol solution of preparation alkali, the volume ratio of pure water is 0: 1～1: 1, the concentration of alkali is 0.001～10 mol, is preferably 0.01～5 mol.
(2). preparation cats product solution, cats product is joined in the solution of step (1), make that the concentration of cetyl trimethyl ammonium halide is 0.001～10 mol in the solution behind the mixed dissolution, be preferably 0.01～1 mol.
(3). silicon ester is joined in the mixing solutions that step (2) obtains, the concentration that makes mixed silicon ester is 0.001～5 mol, be preferably 0.005～1 mol, continue to stir 3～5 hours, get the solution of white precipitate, centrifugation then, washing, drying after 500～700 ℃ of roastings, obtain column mesoporous silicon-dioxide; The length-to-diameter ratio of described column mesoporous silicon-dioxide is 3: 1～1: 1, and column length is 600～200nm, and column diameter is 300～100nm, and specific surface area is 800～1200m
2/ g, the mesoporous 2.0～5.0nm that is of a size of.
Described alkaline solution can be the aqueous solution of alkali or the alcohol solution of alkali; Alcohol is 0: 1～1: 1 with the volume ratio of water in the alcohol solution of described alkali.
Described mineral alkali comprises one or both mixtures of ammoniacal liquor, sodium hydroxide, potassium hydroxide.
Described cetyl trimethyl ammonium halide can be cetyl trimethylammonium bromide or palmityl trimethyl ammonium chloride.
Described silicon ester can be methyl silicate or tetraethoxy.
Purposes of the present invention: end-use of the present invention is extensive, 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.
Adopt column mesoporous earth silicon material that method of the present invention obtains as shown in Figure 1.Method of the present invention not only energy consumption is low, the product purity height, and good dispersity, and the length-to-diameter ratio of column mesoporous silicon-dioxide can be controlled by changing reaction conditions.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 column mesoporous earth silicon material stereoscan photograph of embodiments of the invention 1;
Specific embodiments
Embodiment 1
(1). the alcohol solution of preparation ammoniacal liquor, volume ratio of alcohol to water 0: 1, the concentration of ammoniacal liquor is 0.001 mol.
(2). the solution of preparation cats product, the cats product palmityl trimethyl ammonium chloride is joined in the solution of step (1), make that the concentration of palmityl trimethyl ammonium chloride is 0.01 mol in the solution behind the mixed dissolution.
(3). tetraethoxy is added in the mixing solutions that step (2) obtains, the concentration that makes mixed tetraethoxy is 0.005 mol, continue to stir 3 hours, get the solution of white precipitate, centrifugation then, washing, drying are after 550 ℃ of roastings, obtain column mesoporous silicon-dioxide (about 3: 1 of length-to-diameter ratio, the about 540nm of column length, the about 180nm of column diameter), specific surface area is 850m
2/ g, the mesoporous 2.1nm that is of a size of.
Embodiment 2
(1). the alcohol solution of preparation potassium hydroxide, volume ratio of alcohol to water 1: 4, the concentration of potassium hydroxide is 0.01 mol.
(2). the solution of preparation cats product, the cats product cetyl trimethylammonium bromide is joined in the solution of step (1), make that the concentration of cetyl trimethylammonium bromide is 0.05 mol in the solution behind the mixed dissolution.
(3). tetraethoxy is added in the mixing solutions that step (2) obtains, the concentration that makes mixed tetraethoxy is 0.01 mol, continue to stir 4 hours, get the solution of white precipitate, centrifugation then, washing, drying, after 600 ℃ of roastings, obtain column mesoporous silicon-dioxide, length-to-diameter ratio is 1.2: 1, and column length is 320nm, column diameter 270nm, specific surface area is 1030m
2/ g, the mesoporous 2.7nm that is of a size of.
Embodiment 3
(1). the alcohol solution of preparation ammoniacal liquor, volume ratio of alcohol to water 1: 1, the concentration of ammoniacal liquor is 9 mol.
(2). the solution of preparation cats product, adding cats product cetyl trimethylammonium bromide in step (1) makes that the concentration of cetyl trimethylammonium bromide is 7.0 mol in the solution behind the mixed dissolution.
(3). tetraethoxy is added in the mixing solutions that step (2) obtains, the concentration that makes mixed tetraethoxy is 4.0 mol, continue to stir 4 hours, get the solution of white precipitate, centrifugation then, washing, drying, after 600 ℃ of roastings, obtain column mesoporous silicon-dioxide, length-to-diameter ratio is 2.3: 1, and column length is 450nm, column diameter 200nm, specific surface area is 970m
2/ g, the mesoporous 2.4nm that is of a size of.
Embodiment 4
(1). the alcohol solution of preparation sodium hydroxide, volume ratio of alcohol to water 1: 10, concentration sodium hydroxide is 1 mol.
(2). the solution of preparation cats product, the cats product palmityl trimethyl ammonium chloride is joined in the solution of step (1), make that the concentration of palmityl trimethyl ammonium chloride is 0.1 mol in the solution behind the mixed dissolution.
(3). tetraethoxy is added in the mixing solutions that step (2) obtains, the concentration that makes mixed tetraethoxy is 1.0 mol, continue to stir 3 hours, get the solution of white precipitate, centrifugation then, washing, drying are after 700 ℃ of roastings, obtain column mesoporous silicon-dioxide (about 1: 1 of length-to-diameter ratio, the about 260nm of column length, the about 260nm of column diameter), specific surface area is 1078m
2/ g, the mesoporous 2.3nm that is of a size of.
Embodiment 5
(1). the alcohol solution of preparation ammoniacal liquor, volume ratio of alcohol to water 1: 20, the concentration of ammoniacal liquor is 4 mol.
(2). the solution of preparation cats product, the cats product palmityl trimethyl ammonium chloride is joined in the solution of step (1), make that the concentration of palmityl trimethyl ammonium chloride is 0.03 mol in the solution behind the mixed dissolution.
(3). tetraethoxy is added in the mixing solutions that step (2) obtains, the concentration that makes mixed tetraethoxy is 0.1 mol, continue to stir 4 hours, get the solution of white precipitate, centrifugation then, washing, drying are after 700 ℃ of roastings, obtain column mesoporous silicon-dioxide (about 1.5: 1 of length-to-diameter ratio, the about 420nm of column length, the about 280nm of column diameter), specific surface area is 984m
2/ g, the mesoporous 2.6nm that is of a size of.
Claims (10)
1. column mesoporous silicon-dioxide, it is characterized in that: the length-to-diameter ratio of described column mesoporous silicon-dioxide is 3: 1～1: 1, and column length is 600～200nm, and column diameter is 300～100nm, and specific surface area is 800～1200m
2/ g, the mesoporous 2.0～5.0nm that is of a size of.
2. the preparation method of a column mesoporous silicon-dioxide as claimed in claim 1, it is characterized in that: described method steps comprises:
(1). the alcohol solution of preparation alkali, the volume ratio of pure water is 0: 1～1: 1, the concentration of alkali is 0.001～10 mol;
(2). preparation cats product solution, cats product is joined in the solution of step (1), make that the concentration of cetyl trimethyl ammonium halide is 0.001～10 mol in the solution behind the mixed dissolution;
(3). silicon ester is joined in the mixing solutions that step (2) obtains, the concentration that makes mixed silicon ester is 0.001～5 mol, continues to stir, and gets the solution of white precipitate, centrifugation then, washing, drying obtain column mesoporous silicon-dioxide after the roasting.
3. method as claimed in claim 2 is characterized in that: the length-to-diameter ratio of described column mesoporous silicon-dioxide is 3: 1～1: 1, and column length is 600～200nm, and column diameter is 300～100nm, and specific surface area is 800～1200m
2/ g, the mesoporous 2.0～5.0nm that is of a size of.
4. method as claimed in claim 2 is characterized in that: described maturing temperature is 500～700 ℃.
5. method as claimed in claim 2 is characterized in that: the concentration of alkali is 0.01～10 mol in the described step (1).
6. method as claimed in claim 2 is characterized in that: the concentration of cetyl trimethyl ammonium halide is 0.01～1 mol in described step (2) solution.
7. method as claimed in claim 2 is characterized in that: the concentration of described step (3) silicon ester is 0.005～1 mol.
8. as claim 2 or 5 described methods, it is characterized in that: described mineral alkali comprises one or both mixtures of ammoniacal liquor, sodium hydroxide, potassium hydroxide.
9. as claim 2 or 6 described methods, it is characterized in that: described cetyl trimethyl ammonium halide is cetyl trimethylammonium bromide or palmityl trimethyl ammonium chloride.
10. as claim 2 or 7 described methods, it is characterized in that: described silicon ester is methyl silicate or tetraethoxy.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101973554A (en) * | 2010-09-16 | 2011-02-16 | 昆明理工大学 | Method for preparing mesoporous silica material |
| CN101704527B (en) * | 2009-12-15 | 2013-06-26 | 南开大学 | Monodisperse mesoporous silica nano-particle with controllable appearance and synthesis method thereof |
| CN105110342A (en) * | 2015-07-20 | 2015-12-02 | 清华大学 | Easily soluble solid silicon oxide sphere, preparation method and application thereof |
| CN110526251A (en) * | 2019-08-28 | 2019-12-03 | 贵州大学 | A kind of preparation method of lithium battery silica negative electrode material |
| CN112174148A (en) * | 2020-10-04 | 2021-01-05 | 贵州师范学院 | Method for synthesizing high-purity hexagonal-cylindrical silicon dioxide nano porous material |
| CN112194139A (en) * | 2020-11-12 | 2021-01-08 | 苏州锦艺新材料科技有限公司 | Preparation method of mesoporous rod-like silicon dioxide |
| CN112337469A (en) * | 2021-01-11 | 2021-02-09 | 东营一鸣新材料有限公司 | Columnar porous catalyst carrier and preparation method thereof |
-
2003
- 2003-08-12 CN CN 03153264 patent/CN1264747C/en not_active Expired - Fee Related
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101704527B (en) * | 2009-12-15 | 2013-06-26 | 南开大学 | Monodisperse mesoporous silica nano-particle with controllable appearance and synthesis method thereof |
| CN101973554A (en) * | 2010-09-16 | 2011-02-16 | 昆明理工大学 | Method for preparing mesoporous silica material |
| CN101973554B (en) * | 2010-09-16 | 2012-10-31 | 昆明理工大学 | Method for preparing mesoporous silica material |
| CN105110342A (en) * | 2015-07-20 | 2015-12-02 | 清华大学 | Easily soluble solid silicon oxide sphere, preparation method and application thereof |
| CN105110342B (en) * | 2015-07-20 | 2017-04-12 | 清华大学 | Easily soluble solid silicon oxide sphere, preparation method and application thereof |
| CN110526251A (en) * | 2019-08-28 | 2019-12-03 | 贵州大学 | A kind of preparation method of lithium battery silica negative electrode material |
| CN112174148A (en) * | 2020-10-04 | 2021-01-05 | 贵州师范学院 | Method for synthesizing high-purity hexagonal-cylindrical silicon dioxide nano porous material |
| CN112174148B (en) * | 2020-10-04 | 2022-02-25 | 贵州师范学院 | Method for synthesizing high-purity hexagonal-cylindrical silicon dioxide nano porous material |
| CN112194139A (en) * | 2020-11-12 | 2021-01-08 | 苏州锦艺新材料科技有限公司 | Preparation method of mesoporous rod-like silicon dioxide |
| CN112337469A (en) * | 2021-01-11 | 2021-02-09 | 东营一鸣新材料有限公司 | Columnar porous catalyst carrier and preparation method thereof |
| CN112337469B (en) * | 2021-01-11 | 2021-04-02 | 东营一鸣新材料有限公司 | Columnar porous catalyst carrier and preparation method thereof |
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| CN1264747C (en) | 2006-07-19 |
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