CN103663473A - Ordered dual-mesoporous silica material and preparation method thereof - Google Patents
Ordered dual-mesoporous silica material and preparation method thereof Download PDFInfo
- Publication number
- CN103663473A CN103663473A CN201310659149.6A CN201310659149A CN103663473A CN 103663473 A CN103663473 A CN 103663473A CN 201310659149 A CN201310659149 A CN 201310659149A CN 103663473 A CN103663473 A CN 103663473A
- Authority
- CN
- China
- Prior art keywords
- preparation
- ordered
- silicon material
- earth silicon
- ordered meso
- 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
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- 239000000463 material Substances 0.000 title claims abstract description 17
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 title abstract description 12
- 239000000377 silicon dioxide Substances 0.000 title abstract description 5
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims abstract description 40
- 239000011148 porous material Substances 0.000 claims abstract description 29
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims abstract description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 14
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 11
- 239000010703 silicon Substances 0.000 claims abstract description 11
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 10
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229920000428 triblock copolymer Polymers 0.000 claims abstract description 6
- 239000012429 reaction media Substances 0.000 claims abstract description 3
- 239000002210 silicon-based material Substances 0.000 claims description 25
- 239000000243 solution Substances 0.000 claims description 22
- 238000000034 method Methods 0.000 claims description 12
- 239000007787 solid Substances 0.000 claims description 12
- 238000003756 stirring Methods 0.000 claims description 12
- 239000003795 chemical substances by application Substances 0.000 claims description 9
- 238000012545 processing Methods 0.000 claims description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- 235000019353 potassium silicate Nutrition 0.000 claims description 8
- 238000000605 extraction Methods 0.000 claims description 5
- 239000004094 surface-active agent Substances 0.000 claims description 5
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- 238000000638 solvent extraction Methods 0.000 claims description 4
- 235000009754 Vitis X bourquina Nutrition 0.000 claims description 2
- 235000012333 Vitis X labruscana Nutrition 0.000 claims description 2
- 240000006365 Vitis vinifera Species 0.000 claims description 2
- 235000014787 Vitis vinifera Nutrition 0.000 claims description 2
- 239000007864 aqueous solution Substances 0.000 claims description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 2
- 238000003828 vacuum filtration Methods 0.000 claims description 2
- 238000012360 testing method Methods 0.000 abstract description 6
- 239000004115 Sodium Silicate Substances 0.000 abstract 1
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 abstract 1
- 238000010438 heat treatment Methods 0.000 abstract 1
- 229910052911 sodium silicate Inorganic materials 0.000 abstract 1
- 239000007788 liquid Substances 0.000 description 10
- 239000013335 mesoporous material Substances 0.000 description 9
- 239000000376 reactant Substances 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 239000004809 Teflon Substances 0.000 description 5
- 229920006362 Teflon® Polymers 0.000 description 5
- 239000008367 deionised water Substances 0.000 description 5
- 229910021641 deionized water Inorganic materials 0.000 description 5
- 238000001914 filtration Methods 0.000 description 5
- 238000007789 sealing Methods 0.000 description 5
- 229910001220 stainless steel Inorganic materials 0.000 description 5
- 239000010935 stainless steel Substances 0.000 description 5
- 238000012546 transfer Methods 0.000 description 5
- 238000012512 characterization method Methods 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 230000001105 regulatory effect Effects 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 230000001276 controlling effect Effects 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000010335 hydrothermal treatment Methods 0.000 description 2
- 229910052814 silicon oxide Inorganic materials 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000002336 sorption--desorption measurement Methods 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- 238000007669 thermal treatment Methods 0.000 description 2
- 102220500397 Neutral and basic amino acid transport protein rBAT_M41T_mutation Human genes 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 230000001413 cellular effect Effects 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000013270 controlled release Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000009792 diffusion process 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
- 239000003337 fertilizer Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000005580 one pot reaction Methods 0.000 description 1
- VDGJOQCBCPGFFD-UHFFFAOYSA-N oxygen(2-) silicon(4+) titanium(4+) Chemical group [Si+4].[O-2].[O-2].[Ti+4] VDGJOQCBCPGFFD-UHFFFAOYSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 230000005945 translocation Effects 0.000 description 1
Images
Landscapes
- Silicates, Zeolites, And Molecular Sieves (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
The invention relates to an ordered dual-mesoporous silica material and a preparation method thereof. The ordered dual-mesoporous silica material has a botryoidal morphology, a length of 5 to 15 mu m, two ordered pores, a specific surface area of 444 to 1103 m<2>/g and a total pore volume of 0.55 to 1.44 cm<3>/g, wherein the pore size of one of the ordered pores is 1.5 to 4.2 nm, and the pore size of the other ordered pore is 4.2 to 15 nm. According to the invention, a phosphoric acid solution is used as a reaction medium, the triblock copolymer P123 is used as a template, tetraethoxysilane or sodium silicate is used as a silicon source, and water bath treatment and hydrothermal synthesis are successively carried out so as to prepare the ordered dual-mesoporous silica material. The material prepared in the invention has a stable product structure; after high temperature roasting heat treatment test at a temperature of 900 DEG C for 10 hours and treatment test with 800 DEG C steam for 24 hours, the material can maintain its original morphology and original pore structure, and the reduction rates of both pore shrinkage and the specific surface area are within 5%.
Description
Technical field
The present invention relates to a kind of mesoporous material, particularly relate to a kind of ordered meso-porous material, and the preparation method of this mesoporous material.
Background technology
Mesoporous silicon oxide is the cellular solid of a kind of aperture 2-50nm.Since Mobile company synthesizes after M41S series mesoporous material for 1992 first, because it has that pore passage structure is regular, big or small adjustable, the specific surface area in duct compared with large, hydrothermal stability compared with high, absorption pore volume compared with the advantage such as large, pattern is different people's extensive concern extremely.Except possessing above advantage, also because of it, there is the meso-hole structure of 2 kinds of different pore sizes, and there is its unique performance in double-mesoporous material.For example large mesoporous larger because of aperture in double-mesoporous material, so diffusional resistance is less, can be used as the transport passage of reactant and product, also can reach the selection translocation to material by regulating and controlling its structure; Little mesoporous because of the selectivity that its active sites is more, specific surface is large, catalysis has been had, thereby the place that can be used as reactant absorption and react.Double-mesoporous material, owing to having above advantage, makes it at aspects such as catalyzer preparation, medicine, Controlled Release Fertilizers, have huge potential application.
Order mesoporous synthesizing is generally synthetic by supramolecule self-assembling method, obtains the organic-inorganic composite body that specific Jie sees space structure, then removes tensio-active agent by the method for roasting or extraction, thereby obtain mesoporous material.The supermolecular module agent of the most generally using is nonionic surface active agent, and using hydrochloric acid as solvent (D.Zhao, J.Feng, Q.Huo, et al. Science, 1998,279,548), but by this method single, the aperture of the meso-porous titanium dioxide silicon structure of preparation only has a kind of, the material that cannot synthesize a plurality of apertures, makes it in catalyzer use, have certain defect.The document of preparing of diplopore and multilevel porous structure mesoporous material is also reported to some extent, be mainly other microcosmic by having prepared before adding when synthesising mesoporous or the macropore or be situated between and see material and make its parcel, and then prepare porous structure material (P. Yang, T. Deng, D. Zhao, Science, 1998,282,2244).This preparation method's step is complicated, aperture adjustment is limited, and processing requirement is high, duct order is poor.Thereby, by simple step, synthesize the mesoporous silicon oxide of multilevel ordered pore structure, so far or a popular research topic.
Summary of the invention
The object of this invention is to provide and a kind ofly prepare in order, be more conducive to molecular diffusion and enter and react, purposes is double metaporous silicon dioxide material and preparation method thereof more widely.
Ordered meso-porous earth silicon material of the present invention has string shape grape pattern, and length 5～15 μ m, have two kinds of orderly holes: a kind of aperture 1.5～4.2nm, another kind of aperture 4.2～15nm, material specific surface area 444～1103m
2/ g, total pore volume 0.55～1.44cm
3/ g, is to utilize phosphoric acid solution as reaction medium, and triblock copolymer P123 is template, take tetraethoxy or water glass as silicon source, adopts first water bath processing, the method for Hydrothermal Synthesis prepares again.
Material product Stability Analysis of Structures prepared by the present invention.Through high-temperature roasting thermal treatment in 900 ℃, 10 hours test and 800 ℃ of water vapour, within 24 hours, process test, pattern and pore structure are kept intact, and aperture shrinking percentage and specific surface area rate of descent are all in 5%.
Ordered meso-porous earth silicon material of the present invention prepares according to following processing step.
1). the surfactant templates agent aqueous solution that preparation mass percentage concentration is 1.5～5.7%, pH value to 1.8～2.4 of dropping phosphoric acid regulator solution.
2). in above-mentioned solution, add silicon source, the molecular fraction that makes surfactant templates agent account for silicon source is 0.015～0.025, under rapid stirring, 30～45 ℃ of water bath processing 18～26h.
3). isolate step 2) solid matter that obtains, be dissolved in the phosphoric acid solution of concentration 0.5～13mol/L, to add the quality of solid be 2～8% of phosphoric acid solution quality.
4). by step 3) solution that obtains processes 24～150h in 80～180 ℃ of hydrothermal methods.
5). by step 4) solidliquid mixture that obtains is separated, gained solid, through roasting or solvent extraction, obtains described ordered meso-porous earth silicon material.
Wherein, described surfactivity is triblock copolymer P123, and described silicon source is tetraethoxy or water glass.
Preferably, described roasting is at 500～650 ℃ of roasting 4～8h, and described solvent extraction is to using ethanol or pyridine as extraction agent.
In aforesaid method, the separated isolated by vacuum filtration that preferably adopts of described solidliquid mixture.
The present invention makes solvent with phosphoric acid, triblock copolymer P123 is template, tetraethoxy or water glass are silicon source, by regulating temperature and the acidity of water bath processing, hydrothermal treatment consists, and the mol ratio in P123 and silicon source, can control earth silicon material particle length 5～15 μ m of generation, and produce two kinds of orderly holes, wherein small aperture 1.5～4.2nm, macropore diameter 4.2～15nm, material specific surface area 444～1103m
2/ g, total pore volume 0.55～1.44cm
3/ g changes.
Prepare the method for multi-stage porous or diplopore with tradition and compare, the present invention only need to just prepare ordered meso-porous earth silicon material by regulating and controlling respectively the condition of water bath processing and hydrothermal treatment consists, is a kind of production method of easy, environmental protection.The inventive method does not need first to synthesize a kind of product, wrap up on its basis again realizing the loaded down with trivial details step of synthetic diplopore pore size material, " one pot " synthesizes two kinds of aperture structures, technique is simple, reproducible, the material synthesizing is processed test in 24 hours through high-temperature roasting thermal treatment in 900 ℃, 10 hours test and 800 ℃ of water vapour, and pattern and pore structure are kept intact, aperture shrinking percentage and specific surface area rate of descent are all in 5%, and product structure stability is high.
Accompanying drawing explanation
Fig. 1 is the scanning electron microscope (SEM) photograph of the ordered meso-porous earth silicon material of embodiment 1 preparation.
Fig. 2 is the scanning electron microscope (SEM) photograph of the ordered meso-porous earth silicon material of embodiment 2 preparations.
Fig. 3 is the X-ray small-angle scattering figure of the ordered meso-porous earth silicon material of embodiment 1 preparation.
Fig. 4 is the X-ray small-angle scattering figure of the ordered meso-porous earth silicon material of embodiment 2 preparations.
Fig. 5 is the nitrogen adsorption-desorption graphic representation of the ordered meso-porous earth silicon material of embodiment 2 preparations.
Fig. 6 is the corresponding pore size distribution curve figure obtaining through BJH algorithm of the ordered meso-porous earth silicon material of embodiment 2 preparations.
Embodiment
Below by specific embodiment, further describe feature of the present invention, but the present invention is not limited to following embodiment.
Under 42 ℃ of conditions of bath temperature, 1.5g P123 is dissolved in 47mL deionized water, drip phosphoric acid, regulator solution, to pH=2.0, continues vigorous stirring 6 hours, obtains transparence liquid, adds 3.21g tetraethoxy in liquid, and vigorous stirring is 24 hours at 42 ℃.
Filter, the solid obtaining is dissolved in 60mL 0.8mol/L phosphoric acid solution, transfer in the stainless steel cauldron with teflon lined, sealing, 120 ℃ of standing hydro-thermal reactions 2 days.
Reactant vacuumizing filtration, 45 ℃ are dry, and 550 ℃ of roastings 7 hours, obtain ordered meso-porous earth silicon material white products.
Fig. 1 and Fig. 3 are respectively scanning electron microscope (SEM) photograph and the X-ray small-angle scattering figure of product, and can draw by nitrogen absorption representation: product length approximately 16 μ m, and the product degree of order is very high, and there is diplopore characteristic peak, small aperture is 2.2nm, and macropore diameter is 7.1nm, specific surface area 947m
2/ g, pore capacities is 0.62cm
3/ g.
Under 37 ℃ of conditions of bath temperature, 1.0g P123 is dissolved in 35mL deionized water, drip phosphoric acid, regulator solution, to pH=2.4, continues vigorous stirring 4 hours, obtains transparence liquid, adds 1.17g water glass in liquid, and vigorous stirring is 24 hours at 37 ℃.
Filter, the solid obtaining is dissolved in 45mL 10mol/L phosphoric acid solution, transfer in the stainless steel cauldron with teflon lined, sealing, 100 ℃ of standing hydro-thermal reactions 4 days.
Reactant vacuumizing filtration, 65 ℃ are dry, and 500 ℃ of roastings 6 hours, obtain ordered meso-porous earth silicon material white products.
Fig. 2, Fig. 4, Fig. 5 and Fig. 6 are respectively the pore size distribution curve figure that scanning electron microscope (SEM) photograph, X-ray small-angle scattering figure, nitrogen adsorption-desorption graphic representation and the BJH algorithm of this product obtain, from characterization result: product length approximately 18 μ m, the degree of order is very high, and be diplopore, one of them pore size 3.47nm, another aperture 6.7nm, specific surface area is 563m
2/ g, pore volume is 0.637cm
3/ g.
Under 40 ℃ of conditions of bath temperature, 7.5g P123 is dissolved in 150mL deionized water, drip phosphoric acid, regulator solution, to pH=1.8, continues vigorous stirring 3.5 hours, obtains transparence liquid, adds 10.2g water glass in liquid, and vigorous stirring is 24 hours at 40 ℃.
Filter, the solid obtaining is dissolved in 160mL 7mol/L phosphoric acid solution, transfer in the stainless steel cauldron with teflon lined, sealing, 100 ℃ of standing hydro-thermal reactions 3 days.
Reactant vacuumizing filtration, 65 ℃ of dried overnight, 550 ℃ of roastings 6 hours, obtain ordered meso-porous earth silicon material white products.
Characterization result: product length approximately 17 μ m, the degree of order is very high, and is diplopore, and pore size is respectively 2.66nm and 7.8nm, and specific surface area is 770m
2/ g, pore volume is 0.894cm
3/ g.
Under 37 ℃ of conditions of bath temperature, 2.2g P123 is dissolved in 75mL deionized water, drip phosphoric acid, regulator solution, to pH=1.9, continues vigorous stirring 4 hours, obtains transparence liquid, adds 5.2g tetraethoxy in liquid, and vigorous stirring is 48 hours at 37 ℃.
Filter, the solid obtaining is dissolved in 110mL 4.8mol/L phosphoric acid solution, transfer in the stainless steel cauldron with teflon lined, sealing, 180 ℃ of standing hydro-thermal reactions 2 days.
Reactant vacuumizing filtration, 80 ℃ of dried overnight, take ethanol as extraction agent, and Soxhlet is extracted 12 hours, obtains ordered meso-porous earth silicon material white products.
Characterization result: product length approximately 14 μ m, the degree of order is very high, and is diplopore, and pore size is respectively 3.34nm and 7.9nm, and specific surface area is 983m
2/ g, pore volume is 1.216cm
3/ g.
Under 45 ℃ of conditions of bath temperature, 4.5g P123 is dissolved in 135mL deionized water, drip phosphoric acid, regulator solution, to pH=2.4, continues vigorous stirring 8 hours, obtains transparence liquid, adds 5.1g water glass in liquid, keeps 45 ℃ of vigorous stirring 24 hours.
Filter, the solid obtaining is dissolved in 210mL 13mol/L phosphoric acid solution, transfer in the stainless steel cauldron with teflon lined, sealing, 150 ℃ of standing hydro-thermal reactions 5 days.
Reactant vacuumizing filtration, 65 ℃ are dry, take ethanol as extraction agent, and Soxhlet is extracted 32 hours, obtains ordered meso-porous earth silicon material white products.
Characterization result: product length approximately 6 μ m, the degree of order is very high, and is diplopore, and pore size is respectively 2.94nm and 5.24nm, and specific surface area is 1061m
2/ g, pore volume is 0.973cm
3/ g.
Claims (7)
1. an ordered meso-porous earth silicon material, has string shape grape pattern, and length 5～15 μ m, have two kinds of orderly holes: a kind of aperture 1.5～4.2nm, another kind of aperture 4.2～15nm, material specific surface area 444～1103m
2/ g, total pore volume 0.55～1.44cm
3/ g, is to utilize phosphoric acid solution as reaction medium, and triblock copolymer P123 is template, take tetraethoxy or water glass as silicon source, adopts first water bath processing, the method for Hydrothermal Synthesis prepares again.
2. the preparation method of the ordered meso-porous earth silicon material of claim 1 is according to following processing step preparation:
1). the surfactant templates agent aqueous solution that preparation mass percentage concentration is 1.5～5.7%, pH value to 1.8～2.4 of dropping phosphoric acid regulator solution;
2). in above-mentioned solution, add silicon source, the molecular fraction that makes surfactant templates agent account for silicon source is 0.015～0.025, under rapid stirring, 30～45 ℃ of water bath processing 18～26h;
3). isolate step 2) solid matter that obtains, be dissolved in the phosphoric acid solution of concentration 0.5～13mol/L, to add the quality of solid be 2～8% of phosphoric acid solution quality;
4). by step 3) solution that obtains processes 24～150h in 80～180 ℃ of hydrothermal methods;
5). by step 4) solidliquid mixture that obtains is separated, gained solid, through roasting or solvent extraction, obtains described ordered meso-porous earth silicon material.
3. the preparation method of ordered meso-porous earth silicon material according to claim 2, is characterized in that described surfactivity is triblock copolymer P123.
4. the preparation method of ordered meso-porous earth silicon material according to claim 2, is characterized in that described silicon source is tetraethoxy or water glass.
5. the preparation method of ordered meso-porous earth silicon material according to claim 2, is characterized in that described roasting is at 500～650 ℃ of roasting 4～8h.
6. the preparation method of ordered meso-porous earth silicon material according to claim 2, is characterized in that described solvent extraction is to take ethanol or pyridine to carry out extracting as extraction agent.
7. the preparation method of ordered meso-porous earth silicon material according to claim 2, is characterized in that the separated isolated by vacuum filtration that adopts of described solidliquid mixture.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310659149.6A CN103663473B (en) | 2013-12-09 | 2013-12-09 | Ordered meso-porous earth silicon material and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310659149.6A CN103663473B (en) | 2013-12-09 | 2013-12-09 | Ordered meso-porous earth silicon material and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103663473A true CN103663473A (en) | 2014-03-26 |
| CN103663473B CN103663473B (en) | 2015-08-19 |
Family
ID=50302380
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310659149.6A Expired - Fee Related CN103663473B (en) | 2013-12-09 | 2013-12-09 | Ordered meso-porous earth silicon material and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103663473B (en) |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104071795A (en) * | 2014-07-14 | 2014-10-01 | 太原理工大学 | Preparation method of special-shape ordered mesoporous silicon dioxide material |
| CN104261414A (en) * | 2014-09-25 | 2015-01-07 | 太原理工大学 | Synthesis method of bimodal mesoporous silicon dioxide |
| CN105366682A (en) * | 2014-08-26 | 2016-03-02 | 中国石油化工股份有限公司 | Dual mesoporous silica microsphere and preparation method thereof |
| CN109850910A (en) * | 2019-01-25 | 2019-06-07 | 西北工业大学 | A kind of classifying porous silica and preparation method thereof |
| CN113277519A (en) * | 2021-06-22 | 2021-08-20 | 清华大学 | Silicon dioxide mesoporous material using waste glass as raw material and preparation method and application thereof |
| CN113277520A (en) * | 2021-06-22 | 2021-08-20 | 清华大学 | Silicon dioxide mesoporous material and preparation method and application thereof |
| CN115703637A (en) * | 2021-08-10 | 2023-02-17 | 中国石油化工股份有限公司 | Porous silicon oxide and preparation method and application thereof |
| CN115703637B (en) * | 2021-08-10 | 2024-07-09 | 中国石油化工股份有限公司 | Porous silicon oxide and preparation method and application thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1648044A (en) * | 2005-01-10 | 2005-08-03 | 山西大学 | Double metaporous silicon dioxide material and its preparing method |
| CN1872684A (en) * | 2006-06-16 | 2006-12-06 | 清华大学 | Method for synthesizing microspheres of high ordered mesoporous silicon dioxide |
| CN101837981A (en) * | 2010-04-30 | 2010-09-22 | 南开大学 | Multilevel porous structure mesoporous silica material and preparation method thereof |
-
2013
- 2013-12-09 CN CN201310659149.6A patent/CN103663473B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1648044A (en) * | 2005-01-10 | 2005-08-03 | 山西大学 | Double metaporous silicon dioxide material and its preparing method |
| CN1872684A (en) * | 2006-06-16 | 2006-12-06 | 清华大学 | Method for synthesizing microspheres of high ordered mesoporous silicon dioxide |
| CN101837981A (en) * | 2010-04-30 | 2010-09-22 | 南开大学 | Multilevel porous structure mesoporous silica material and preparation method thereof |
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104071795A (en) * | 2014-07-14 | 2014-10-01 | 太原理工大学 | Preparation method of special-shape ordered mesoporous silicon dioxide material |
| CN105366682A (en) * | 2014-08-26 | 2016-03-02 | 中国石油化工股份有限公司 | Dual mesoporous silica microsphere and preparation method thereof |
| CN105366682B (en) * | 2014-08-26 | 2018-11-30 | 中国石油化工股份有限公司 | A kind of double-mesopore silicon dioxide microballoon and preparation method |
| CN104261414A (en) * | 2014-09-25 | 2015-01-07 | 太原理工大学 | Synthesis method of bimodal mesoporous silicon dioxide |
| CN104261414B (en) * | 2014-09-25 | 2016-01-20 | 太原理工大学 | A kind of synthetic method of double-mesopore silicon dioxide |
| CN109850910A (en) * | 2019-01-25 | 2019-06-07 | 西北工业大学 | A kind of classifying porous silica and preparation method thereof |
| CN109850910B (en) * | 2019-01-25 | 2020-09-25 | 西北工业大学 | Preparation method of hierarchical porous silicon oxide |
| CN113277519A (en) * | 2021-06-22 | 2021-08-20 | 清华大学 | Silicon dioxide mesoporous material using waste glass as raw material and preparation method and application thereof |
| CN113277520A (en) * | 2021-06-22 | 2021-08-20 | 清华大学 | Silicon dioxide mesoporous material and preparation method and application thereof |
| CN113277520B (en) * | 2021-06-22 | 2022-09-16 | 清华大学 | Silicon dioxide mesoporous material and preparation method and application thereof |
| CN115703637A (en) * | 2021-08-10 | 2023-02-17 | 中国石油化工股份有限公司 | Porous silicon oxide and preparation method and application thereof |
| CN115703637B (en) * | 2021-08-10 | 2024-07-09 | 中国石油化工股份有限公司 | Porous silicon oxide and preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103663473B (en) | 2015-08-19 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103663473B (en) | Ordered meso-porous earth silicon material and preparation method thereof | |
| EP2878366A1 (en) | Mesoporous metal-organic frameworks with dominating interparticular porosity, methods for preparation thereof and uses | |
| AU2012258092B2 (en) | Process for producing inorganic particulate material | |
| Su et al. | Synthesis and characterization of monodisperse porous α-Al2O3 nanoparticles | |
| Sarawade et al. | Synthesis and characterization of micrometer-sized silica aerogel nanoporous beads | |
| CN104607231A (en) | Carbon nitride photocatalyst with three-dimensional ordered macroporous structure and preparation method thereof | |
| Kishor et al. | Understanding the hydrothermal, thermal, mechanical and hydrolytic stability of mesoporous KIT-6: a comprehensive study | |
| Misran et al. | Nonsurfactant route of fatty alcohols decomposition for templating of mesoporous silica | |
| Sánchez-Sánchez et al. | pH-responsive ordered mesoporous carbons for controlled ibuprofen release | |
| Zucchetto et al. | The structure of mesoporous silica obtained by pseudomorphic transformation of SBA-15 and SBA-16 | |
| Alapi et al. | Synthesis and characterization of titania photocatalysts: the influence of pretreatment on the activity | |
| CN102874823A (en) | Method for preparing silicon dioxide hollow microspheres with uniform shape by taking pollen grains as biological template | |
| Shao et al. | Rapid synthesis of amine cross-linked epoxy and methyl co-modified silica aerogels by ambient pressure drying | |
| Prabhu et al. | Synthesis and characterization of mesoporous carbon by simple one pot method | |
| Liu et al. | Gelatin-assisted sol–gel derived TiO2 microspheres for hydrogen storage | |
| Wang et al. | Unit-cell wide SBA-15 type mesoporous silica nanoparticles | |
| CN101811702A (en) | Double-mesopore silicon dioxide transparent gel monolith and preparation method thereof | |
| CN102153059B (en) | Method for preparing monodisperse hydroxyapatite by taking blue algae as template | |
| Ma et al. | Hierarchical porous bioactive glasses/PLGA-magnetic SBA-15 for dual-drug release | |
| Sun et al. | Triblock copolymer and poly (ethylene glycol) as templates for monolithic silica material with bimodal pore structure | |
| CN102285659B (en) | Ordered mesoporous silicon-dioxide material and preparation method thereof | |
| Nowak | Textural and structural properties of niobium-containing micro-, meso-and macroporous molecular sieves | |
| JP2007223857A (en) | Method for producing porous structure and porous structure | |
| US10577250B2 (en) | Process for producing of inorganic particulate material | |
| Ma et al. | Tailoring porosity and dimensionality of Co3O4 nanophase using channel interconnectivity control by steaming of nanocasting SBA-15 |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | 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: 20150819 |