CN101723396A - Hexagonal flaky sequential silicon-based mesoporous material SBA-15 and preparation method thereof - Google Patents
Hexagonal flaky sequential silicon-based mesoporous material SBA-15 and preparation method thereof Download PDFInfo
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- CN101723396A CN101723396A CN200910199537A CN200910199537A CN101723396A CN 101723396 A CN101723396 A CN 101723396A CN 200910199537 A CN200910199537 A CN 200910199537A CN 200910199537 A CN200910199537 A CN 200910199537A CN 101723396 A CN101723396 A CN 101723396A
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- 239000013335 mesoporous material Substances 0.000 title claims abstract description 45
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 title claims abstract description 23
- 229910052710 silicon Inorganic materials 0.000 title claims abstract description 23
- 239000010703 silicon Substances 0.000 title claims abstract description 23
- 238000002360 preparation method Methods 0.000 title abstract description 16
- 239000011148 porous material Substances 0.000 claims abstract description 23
- 238000000034 method Methods 0.000 claims abstract description 15
- 238000006243 chemical reaction Methods 0.000 claims abstract description 13
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 10
- 239000013543 active substance Substances 0.000 claims description 9
- 239000002243 precursor Substances 0.000 claims description 9
- 238000003756 stirring Methods 0.000 claims description 8
- 239000000047 product Substances 0.000 claims description 4
- 238000002425 crystallisation Methods 0.000 claims description 3
- 230000008025 crystallization Effects 0.000 claims description 3
- 238000001914 filtration Methods 0.000 claims description 3
- 239000012467 final product Substances 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 7
- 229920003171 Poly (ethylene oxide) Polymers 0.000 abstract description 3
- -1 polyethylene Polymers 0.000 abstract description 3
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 abstract 2
- 239000003795 chemical substances by application Substances 0.000 abstract 2
- 239000004094 surface-active agent Substances 0.000 abstract 2
- 239000004698 Polyethylene Substances 0.000 abstract 1
- 239000004743 Polypropylene Substances 0.000 abstract 1
- 239000007810 chemical reaction solvent Substances 0.000 abstract 1
- 239000008367 deionised water Substances 0.000 abstract 1
- 229910021641 deionized water Inorganic materials 0.000 abstract 1
- 229920000573 polyethylene Polymers 0.000 abstract 1
- 229920001155 polypropylene Polymers 0.000 abstract 1
- 238000006555 catalytic reaction Methods 0.000 description 3
- 239000003292 glue Substances 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- 235000012791 bagels Nutrition 0.000 description 2
- 230000033558 biomineral tissue development Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 239000002808 molecular sieve Substances 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 2
- 244000226021 Anacardium occidentale Species 0.000 description 1
- 238000000018 DNA microarray Methods 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 241000950638 Symphysodon discus Species 0.000 description 1
- 241000209140 Triticum Species 0.000 description 1
- 235000021307 Triticum Nutrition 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000012620 biological material Substances 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000003592 biomimetic effect Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 235000020226 cashew nut Nutrition 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 238000013270 controlled release Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000014509 gene expression Effects 0.000 description 1
- HOQADATXFBOEGG-UHFFFAOYSA-N isofenphos Chemical compound CCOP(=S)(NC(C)C)OC1=CC=CC=C1C(=O)OC(C)C HOQADATXFBOEGG-UHFFFAOYSA-N 0.000 description 1
- 239000008204 material by function Substances 0.000 description 1
- 239000011858 nanopowder Substances 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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Abstract
The invention relates to a hexagonal flaky sequential silicon-based mesoporous material SBA-15 and a preparation method thereof. The material is prepared by using a commercial surfactant polyethylene oxide-polypropylene oxide-polyethylene oxide (EO20-PO70-EO20) as a template agent, using tetraethoxysilane (TEOS) as a silicon source and using hydrochloric acid-deionized water as a reaction solvent through the reaction for 26 to 72 hours at the temperature of between 60 and 140 DEG C. The prepared SBA-15 has a two-dimensional hexagonal structure; the products have uniform appearance, namely hexagonal flaky appearance with diameter of between 1 and 1.6 microns and thickness of between 0.2 and 0.6 micron; the material has a pore structure with sequential height, adjustable pore diameter of between 6 and 8 nm, specific surface area of between 680 and 720 m2/g and pore volume of between 1.0 and 1.2 cm3/g. The method is characterized in that: the SBA-15 prepared under the reaction condition has a uniform hexagonal flaky appearance and a pore structure with sequential height and good hydrothermal stability; and the method is economical and environment-friendly due to the adoption of the commercial and environment-friendly surfactant serving as the template agent.
Description
Technical field
The present invention relates to sequential silicon-based mesoporous material and preparation method thereof, specially refer to sequential silicon-based mesoporous material SBA-15 of the thin shape pattern of a kind of six side's sheets and preparation method thereof.
Technical background
Orderly mesoporous material is meant that the supramolecular structure that forms with tensio-active agent is a template, utilize sol-gel technology, a class aperture that is assembled into by the interface directional guide effect between organism and the inorganics at 2～50nm, pore size distribution is narrower and inorganic porous material with regular pore canal structure.It has that high specific surface area, duct are uniform sequential, the aperture can be in 2～50nm scope characteristic such as adjusting continuously, make it have multiple potential purposes in fields such as separating purification, biomaterial, chemical industry, catalysis, information communication, environment, the energy, novel assembled material, especially mesoporous material has broad application prospects at aspects such as the embedding of bio-science such as fixedly separation of protein, biochip, biosensor, medicine and controlled releases.Therefore, found that from 1992 ordered mesoporous material receives much attention in international physics, chemistry and material educational circles since the ordered mesoporous material M41s (Nature.359 (1992), 710-712).
With regard to practical application, as: absorption, separation and catalysis, photoconductive fiber, chromatogram, and the exploitation of new bio functional materials or the like, effective application of mesoporous material is not only relevant with its intrinsic pore passage structure, more macroscopical with it form, microscopic appearance close ties.And say that from academic research the control of ordered mesoporous material pattern and biomineralization, biomimetic chemistry or the like have certain dependency.Therefore, since the research of the pattern of mesoporous material is found from mesoporous material, just become a big focus of mesoporous material research field.
Mesoporous material with definite shape is a multilevel hierarchy body, can regard the orderly assembly of meso-hole structure unit (nanoscale) in micro-meter scale as.The generation of the different shape mesoporous material of micro-meter scale is considered to and the biomineralization similar process; And the material that contains the spacious pore structure of nanometer of micro-meter scale has tangible dimensional effect, influences the mass-transfer efficiency in catalysis, separation, the adsorption process.Therefore, morphology control at this yardstick (Adv.Mater.9 (1997) that especially receives publicity, 254, J.Mater.Chem.8 (1998), 743, Chem.Mater.14 (2002), 4721, Angew.Chem.Int.Ed.41 (2002), 2590.) o is because the complicacy of self assembling process, the adjustable sex change of system makes mesoporous material can have abundant more form to exist.The forms (Nature.386 (1997), 692.) in different poses and with different expressions such as dial plate shape that can have disc, volution, rope, petal, diatom shape, hollow tubular, annular, discus shape, wheel shape, windmill shape, bagel, shell-like, knot shape, clock and watch such as MCM-41; And the pattern of SBA-15 can obtain bodies (Chem.Mater.12 (2000), 275.) such as wheat head shape, cashew nut shape, fiber, annulus, rope form, dish shape, bagel according to synthesis condition.
Summary of the invention
The object of the present invention is to provide a kind of sequential silicon-based mesoporous material SBA-15 with the laminar pattern of even six sides.
Two of purpose of the present invention is to provide this preparation methods.
For achieving the above object, the present invention adopts following technical scheme:
A kind of hexagonal flaky sequential silicon-based mesoporous material SBA-15 is characterized in that this mesoporous material has the regular laminar pattern of six sides, and diameter is at 1.0～1.6 μ m, and its thickness is 0.2～0.6 μ m; Meso-hole structure is a linear pattern, and the aperture is 6～8nm, is typical two dimension six side's mesoscopic structures.
The specific surface area of above-mentioned mesoporous material is 680～720m
2/ g, pore volume are 1.00～1.20cm
3/ g.
A kind of method for preparing above-mentioned hexagonal flaky sequential silicon-based mesoporous material SBA-15 is characterized in that these method concrete steps are:
A. prepare pH and be 1～3 aqueous hydrochloric acid, by 1: the mass ratio of (2～3) adds tensio-active agent P123 and tetraethoxy, stirs 1～2 hour down in 30 ℃～40 ℃, promptly gets collosol and gel shape reaction precursor body;
B. the reaction precursor body that step a is made was in 60～140 ℃ of following hydrothermal crystallizings 1～2 day, the crystallization after product after filtration, washing, drying, calcined 4～10 hours down at 500～650 ℃ at last, remove tensio-active agent, promptly obtain the final product hexagonal flaky sequential silicon-based mesoporous material SBA-15.
Compared with prior art, the characteristics of the prepared hexagonal flaky sequential silicon-based mesoporous material SBA-15 of the present invention are:
1) prepared nano-powder is a hexagonal flaky sequential silicon-based mesoporous material SBA-15, product pattern homogeneous (regular hexagonal flake pattern is all arranged), its diameter is at 1.0～1.6 μ m, its thickness is 0.2～0.6 μ m, this material has the pore structure of high-sequential, has typical two-dimentional six side's mesoscopic structures.
2) be template with commercialization and environment amenable tensio-active agent polyethylene oxide one poly(propylene oxide) one polyethylene oxide, so this synthetic method is economic environmental protection.
3) the mesopore molecular sieve hydrothermal stability height of this method preparation.
The hexagonal flaky sequential silicon-based mesoporous material SBA-15 of the new pattern that the present invention is prepared not only provides a kind of more effectively mesoporous material for relevant practical application; Say that from academic research the discovery of this new pattern also is that the formation mechanism (J.Am.Chem.Soc.114 (1992), 10834, Chem.Mater.6 (1994), 1176.) of mesoporous material provides strong proof directly perceived.
Description of drawings
Fig. 1 is the XRD figure spectrum of the hexagonal flaky sequential silicon-based mesoporous material SBA-15 of embodiment 1 preparation
Fig. 2 is the hexagonal flaky sequential silicon-based mesoporous material SBA-15 transmission electron microscope (TEM) and scanning electron microscope (SEM) figure of embodiment 1 preparation
Fig. 3 is the N of the hexagonal flaky sequential silicon-based mesoporous material SBA-15 of embodiment 1 preparation
2Adsorption curve and graph of pore diameter distribution
Fig. 4 is the TEM figure of the hexagonal flaky sequential silicon-based mesoporous material SBA-15 of embodiment 2 preparations
Fig. 5 is the TEM figure of the hexagonal flaky sequential silicon-based mesoporous material SBA-15 of embodiment 3 preparations
Embodiment
Below in conjunction with examples of implementation the present invention is done more specifically detailed explanation.
The preparation of the first step reaction precursor body:
Preparation pH is 1 aqueous hydrochloric acid, adds tensio-active agent P123 and stirs 30min down in 30 ℃, adds the 4.3g tetraethoxy, stirs 10h down in 30 ℃, promptly gets reaction precursor body glue;
The second step hydrothermal crystallizing
The reaction precursor body that previous step is made places autoclave, in 100 ℃ of following hydrothermal crystallizings 2 days, the good product of crystallization after filtration, washing, and in 100 ℃ of following dry 24h, in retort furnace, under 500～650 ℃, calcine 6h at last, remove template, promptly obtain final product hexagonal flake SBA-15.
Referring to Fig. 1, Fig. 1 is corresponding with the XRD figure spectrum of the ordered mesoporous material SBA-15 of bibliographical information for the prepared hexagonal flaky sequential mesoporous material XRD figure spectrum of the present invention, proves that synthetic resulting ordered mesoporous material is SBA-15.
Referring to Fig. 2, Fig. 1 can find out clearly that this ordered mesoporous material SBA-15 has the hexagonal flake pattern of even rule, and productive rate is very high for TEM and the SEM photo of the used ordered mesoporous material SBA-15 of the present invention.
Referring to accompanying drawing 3,, as can be seen from the figure the SBA-15 of synthetic gained has IV type adsorption curve, proves that this material has typical linear pattern pore structure, pore size distribution is very narrow as can be seen from graph of pore diameter distribution; The mean pore size of sample, BET specific surface area and pore volume are respectively 6.78nm, 689.0m
2/ g and 1.02m
3/ g.Sample was boiled 6 days in 100 ℃ of boiling water, and obvious change does not take place in its structure, illustrates that the synthetic mesopore molecular sieve has high hydrothermal stability.
The preparation of the first step reaction mixture
Operating process except for the following differences, all the other are with embodiment 1.
Regulate pH to 1.5 with hydrochloric acid, add tensio-active agent 2.0g P123 and stir 50min down, add the 4.3g tetraethoxy, stir 14h down, promptly get reaction precursor body glue in 36 ℃ in 35 ℃;
The second step hydrothermal crystallizing
With embodiment 1.
Compare with embodiment 1, after reaction conditions changes in the building-up process, gained still be the even hexagonal flake pattern of rule, but its microscopic appearance diameter becomes greatly, pore structure also changes concrete data to some extent referring to table 1.
Embodiment 3
The preparation of the first step reaction mixture
Operating process except for the following differences, all the other are with embodiment 1.
Regulate pH to 2.0 with hydrochloric acid, add tensio-active agent P123 and stir 70min down, add the 4.3g tetraethoxy, stir 14h down, promptly get reaction precursor body glue in 46 ℃ in 50 ℃;
The second step hydrothermal crystallizing
Operating process is with embodiment 1.
Compare with embodiment 1, after reaction conditions changes in the building-up process, gained still be the even hexagonal flake pattern of rule, but its microscopic appearance diameter becomes greatly, pore structure also changes concrete data to some extent referring to table 1.
The pore structure of table 1 hexagonal flaky sequential silicon-based mesoporous material SBA-15 and microscopic appearance diameter variation thereof
| Embodiment | Mean pore size (nm) | BET surface-area (m 2/g) | Pore volume (cm 3/g) | Hexagonal flake diameter (nm) |
| |
??6.74 | ??689.0 | ??1.02 | ??1.10 |
| |
??6.98 | ??660.2 | ??1.03 | ??1.20 |
| Embodiment 3 | ??7.10 | ??630.2 | ??1.17 | ??1.40 |
Claims (3)
1. the thin shape sequential silicon-based mesoporous material SBA-15 of side's sheet is characterized in that this mesoporous material has the regular laminar pattern of six sides, and diameter is at 1.0～1.6 μ m, and its thickness is 0.2～0.6 μ m; Meso-hole structure is a linear pattern, and the aperture is 6～8nm, is typical two dimension six side's mesoscopic structures.
2. hexagonal flaky sequential silicon-based mesoporous material SBA-15 according to claim 1, the specific surface area that it is characterized in that described mesoporous material is 680～720m
2/ g, pore volume are 1.00～1.20cm
3/ g.
3. method for preparing hexagonal flaky sequential silicon-based mesoporous material SBA-15 according to claim 1 is characterized in that these method concrete steps are:
A. prepare pH and be 1～3 aqueous hydrochloric acid, by 1: the mass ratio of (2～3) adds tensio-active agent P123 and tetraethoxy, stirs 1～2 hour down in 30 ℃～40 ℃, promptly gets collosol and gel shape reaction precursor body;
B. the reaction precursor body that step a is made was in 60～140 ℃ of following hydrothermal crystallizings 1～2 day, the crystallization after product after filtration, washing, drying, calcined 4～10 hours down at 500～650 ℃ at last, remove tensio-active agent, promptly obtain the final product hexagonal flaky sequential silicon-based mesoporous material SBA-15.
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102033028A (en) * | 2010-09-21 | 2011-04-27 | 上海大学 | Preparation method of mass type formaldehyde sensor based on functionalized SBA-15 |
| CN102952211A (en) * | 2011-08-25 | 2013-03-06 | 中国石油化工股份有限公司 | Supported metallocene catalyst and preparation method and application thereof |
| CN103588219A (en) * | 2013-11-11 | 2014-02-19 | 华东理工大学 | Method for enlarging aperture of mesoporous material SBA-15 and effectively removing template agent, and mesoporous material |
| CN103896338A (en) * | 2014-03-24 | 2014-07-02 | 上海大学 | Method for preparing tungsten trioxide with regular hexagonal flaky morphology by using template method and application thereof |
| CN104016369A (en) * | 2014-06-04 | 2014-09-03 | 内蒙古大学 | Method for synthesizing high-stability ordered mesoporous material A1-SBA-15 by use of kaoline |
| CN105084382A (en) * | 2014-05-08 | 2015-11-25 | 中国石油化工股份有限公司 | Mesoporous titanosilicate material and synthesizing method thereof |
| CN107649097A (en) * | 2017-10-30 | 2018-02-02 | 上海泰坦科技股份有限公司 | A kind of method of modifying of the mesoporous materials of SBA 15 |
| CN107970901A (en) * | 2017-10-30 | 2018-05-01 | 上海泰坦科技股份有限公司 | A kind of synthetic method of SBA-15 mesoporous materials |
| CN108659261A (en) * | 2018-04-29 | 2018-10-16 | 王金桢 | A kind of preparation method of catalysis makrolon degradation Molecular Sieves as Template material |
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2009
- 2009-11-26 CN CN2009101995374A patent/CN101723396B/en not_active Expired - Fee Related
Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102033028B (en) * | 2010-09-21 | 2012-08-29 | 上海大学 | Preparation method of mass type formaldehyde sensor based on functionalized SBA-15 |
| CN102033028A (en) * | 2010-09-21 | 2011-04-27 | 上海大学 | Preparation method of mass type formaldehyde sensor based on functionalized SBA-15 |
| CN102952211B (en) * | 2011-08-25 | 2014-11-05 | 中国石油化工股份有限公司 | Supported metallocene catalyst and preparation method and application thereof |
| CN102952211A (en) * | 2011-08-25 | 2013-03-06 | 中国石油化工股份有限公司 | Supported metallocene catalyst and preparation method and application thereof |
| CN103588219A (en) * | 2013-11-11 | 2014-02-19 | 华东理工大学 | Method for enlarging aperture of mesoporous material SBA-15 and effectively removing template agent, and mesoporous material |
| CN103588219B (en) * | 2013-11-11 | 2015-07-01 | 华东理工大学 | Method for enlarging aperture of mesoporous material SBA-15 and effectively removing template agent, and mesoporous material |
| CN103896338A (en) * | 2014-03-24 | 2014-07-02 | 上海大学 | Method for preparing tungsten trioxide with regular hexagonal flaky morphology by using template method and application thereof |
| CN105084382A (en) * | 2014-05-08 | 2015-11-25 | 中国石油化工股份有限公司 | Mesoporous titanosilicate material and synthesizing method thereof |
| CN105084382B (en) * | 2014-05-08 | 2017-09-26 | 中国石油化工股份有限公司 | A kind of mesoporous titanium-silicon material and its synthetic method |
| CN104016369A (en) * | 2014-06-04 | 2014-09-03 | 内蒙古大学 | Method for synthesizing high-stability ordered mesoporous material A1-SBA-15 by use of kaoline |
| CN104016369B (en) * | 2014-06-04 | 2016-01-06 | 内蒙古大学 | A kind of method utilizing kaolin synthesizing high-stability ordered mesoporous material Al-SBA-15 |
| CN107649097A (en) * | 2017-10-30 | 2018-02-02 | 上海泰坦科技股份有限公司 | A kind of method of modifying of the mesoporous materials of SBA 15 |
| CN107970901A (en) * | 2017-10-30 | 2018-05-01 | 上海泰坦科技股份有限公司 | A kind of synthetic method of SBA-15 mesoporous materials |
| CN108659261A (en) * | 2018-04-29 | 2018-10-16 | 王金桢 | A kind of preparation method of catalysis makrolon degradation Molecular Sieves as Template material |
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Date of cancellation: 20190412 Granted publication date: 20110810 Pledgee: Xinxiang Henan plain rural commercial bank Limited by Share Ltd Pledgor: HENAN SHENGMASI SCIENCE & TECHNOLOGY CO., LTD. Registration number: 2016990001113 |