CN100406380C - Method of synthesizing ordered mesoporous silica dioxide using cation alkyl glycoside as template agent - Google Patents
Method of synthesizing ordered mesoporous silica dioxide using cation alkyl glycoside as template agent Download PDFInfo
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- CN100406380C CN100406380C CNB2006100297456A CN200610029745A CN100406380C CN 100406380 C CN100406380 C CN 100406380C CN B2006100297456 A CNB2006100297456 A CN B2006100297456A CN 200610029745 A CN200610029745 A CN 200610029745A CN 100406380 C CN100406380 C CN 100406380C
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Abstract
This invention rerlates to a method for preparing orderly mesoporous silicon dioxide material by using anion alkyl glucoside as template. Said method comprises mixing the template and water at a certain pH, then adding silicon resource and stirring, washing, drying, and calcining to obtain the final silicon dioxide material with good thermal stability and hydrothermal stability.
Description
Technical field
The invention belongs to the inorganic porous material technical field, being specifically related to a kind of is the method for the synthesizing ordered mesoporous SiO2 material of template with the CAPG tensio-active agent.
Background technology
The scientist of Mobil in 1992 expands to mesoporous field for the synthetic regular aperture with material of M41S series silicon-based mesoporous material from range of micropores.Ordered mesoporous material has a class novel material of wide application prospect.Many research fields such as it is sent at the catalyzer, semi-conductor, optics, computer, senser element, the medicine that separate purification, biomaterial, chemosynthesis and conversion, gas and liquid adsorption have wide application prospect.
At present, having periodically, the Metaporous silicon dioxide material in duct can synthesize under multiple condition.The PH scope of synthetic medium non-constant width from the strongly-acid to the high alkalinity, synthesis temperature are from about the room temperature to 150 ℃, and structure directing agent can be positively charged ion, negatively charged ion, nonionogenic tenside, also can be some nonsurfactant materials.
Wherein be with the cats product template synthesize meso-porous material the most frequently used be the agent of living of low-molecular-weight long chain alkyl ammonium salt type cationic surface.People such as Cai Q use the cats product of this long chain alkyl ammonium salt type to synthesize the MCM-41 mesoporous material [document: Cai Q of high-sequential, Lin W Y, Xiao F S et al.The preparation of highlyordered MCM-41 with extremely low surfactant concentration, Microporous Mesoporous Mater.1999,32:1-5].But this tensio-active agent is more single as the mesoporous material structure that template synthesizes, and hole wall is thinner, and hydrothermal stability is relatively poor, and thermostability is relatively low.In addition, people such as Huo Q S use the bigger chain alkyl triethyl ammonium cats product of polar head to synthesize the SBA-1[document in the strongly-acid medium: Huo Q S, Margolese D I, Ciesla Uet al.Generalized Synthesis of Periodic Surfactant Inorganic Composite Materials, Nature.1994,368:317-321], Leontidis E uses Gemini (C
N-s-m) two valency cationic surfactants of type have synthesized the three-dimensional six side's phase product S BA-2[documents that contain basket structure: Leontidis E.Hofmeister anion effects on surfactant self-assembly and the formation of mesoporous solids, Curr Opin Colloid Interface Sci.2002,7:81-91].People such as Zhao D Y use the tensio-active agent that contains rigid radical in the bola type hydrocarbon chain as the template SBA-8[document that is synthesized: Zhao D Y, Huo Q S, Feng J L et al.Novel mesoporous silicates withtwo-dimensional mesostructure direction using rigid bolaform surfactants, ChemMater.1999,11:2668-2672], people such as Stucky G D use speciality chain double end quaternary ammonium salt cationic tensio-active agent to synthesize the SBA-6[document as template in alkaline medium: Stucky G D, Huo Q S, Firouzi A et al.Directed synthesisof organic/inorganic composites structures, Progress in Zeolite and Microporous Materials, 1997.3-28], people such as Qisheng Huo have also reported to use contains phenyl ring or siliceous cats product synthesize different structure as template Metaporous silicon dioxide material [document: Qisheng Huo Qisheng Huo, David I.Margolese, and Galen D.Stucky Chem.Mater.1996,8,1147-1160].Seek novel, particularly eco-friendly tensio-active agent, the synthetic orderly earth silicon material of guiding with new texture, improving the hydrothermal stability of synthetic materials and thermostability etc. is one of focus of present Metaporous silicon dioxide material.
Summary of the invention
At the deficiency that prior art exists, the object of the present invention is to provide a kind of is template with the CAPG tensio-active agent, the method for synthesizing ordered mesoporous silica dioxide material, and this synthetic method is simple, generated time weak point and environmentally friendly.
Goal of the invention of the present invention is achieved through the following technical solutions:
A kind of is template with the CAPG tensio-active agent, and the method for synthesizing ordered mesoporous silica dioxide material is to be structure directing agent with the CAPG tensio-active agent, under alkaline condition the quick hydrolysis in silicon source is obtained.Concrete steps are as follows: be 0.4～4: 10～50 with mass ratio at first: mix in 0.5～2: 1～4 CAPG tensio-active agent, water, alkali or acid, silicon source, stir down at 10～70 ℃, stirred 4～24 hours, direct filtration washing then, after 25～100 ℃ of dryings, and form 350 ℃～550 ℃ roastings, can obtain the cubic mesoporous earth silicon material of d value at 2～14nm.
In the aforesaid method, cats product is the 50% CAPG aqueous solution.The silicon source is tetraethoxy or water glass.Used alkali is ammoniacal liquor, sodium hydroxide etc., and acid is acetic acid, sulfuric acid etc.
Advantage of the present invention is:
1, synthetic method is simple, and generated time is short, and is easy to operate.
2, synthetic ordered mesoporous silica dioxide material of the present invention has good thermostability and hydrothermal stability.Handled in 100 ℃ of hot water 60 hours and 900 ℃ of nitrogen in roasting still can keep ordered structure after 2 hours.
3, the structure directing agent that the present invention uses is the technical grade CAPG, has environment amenable characteristics, helps the industrialization of product.
Embodiment
Embodiment 1
CAPG tensio-active agent (CAPG-08143) with 50%, water, 1M ammoniacal liquor, tetraethoxy are 0.9: 20: 1.1 by mass ratio: 2 mix, 19 ℃ of stirrings, stirred 10 hours, and filtered deionized water rinsing, after 80 ℃ of dryings, roasting is 4 hours in 350 ℃ of air, obtains the white powder product, and productive rate is 90%, can obtain the mesoporous silicon oxide of cube phase, the d value is 6.3nm.
Embodiment 2
CAPG tensio-active agent (CAPG-12143) with 50%, water, 1M ammoniacal liquor, tetraethoxy are 0.6: 20: 1.1 by mass ratio: 2 mix, 50 ℃ of stirrings, stirred 10 hours, and filtered deionized water rinsing, after 60 ℃ of dry airs, roasting is 4 hours in 500 ℃ of air, obtains the white powder product, and productive rate is 87%, can obtain the mesoporous silicon oxide of cube phase, the d value is 5.5nm.
Embodiment 3
CAPG tensio-active agent (CAPG-12143) with 50%, water, 1M ammoniacal liquor, tetraethoxy are 1.2: 20: 1.1 by mass ratio: 2 mix, 13 ℃ of stirrings, stirred 10 hours, and filtered deionized water rinsing, after 80 ℃ of dry airs, roasting is 4 hours in 550 ℃ of air, obtains the white powder product, and productive rate is 88%, can obtain the mesoporous silicon oxide of cube phase, the d value is 7.4nm.
Embodiment 4
CAPG tensio-active agent (CAPG-08143) with 50%, water, Glacial acetic acid, water glass are 0.9: 20: 0.78 by mass ratio: 2.73 mix, 19 ℃ of stirrings, stirred 12 hours, and filtered deionized water rinsing, after 80 ℃ of dryings, roasting is 4 hours in 450 ℃ of air, obtains the white powder product, and productive rate is 90%, can obtain the mesoporous silicon oxide of cube phase, the d value is 8.1nm.
Embodiment 5
CAPG tensio-active agent (CAPG-08143) with 50%, water, Glacial acetic acid, water glass are 0.9: 20: 0.78 by mass ratio: 2.73 mix, 30 ℃ of stirrings, stirred 9 hours, and filtered deionized water rinsing, after 30 ℃ of dryings, roasting is 4 hours in 350 ℃ of air, obtains the white powder product, and productive rate is 90%, can obtain the mesoporous silicon oxide of cube phase, the d value is 8.8nm.
Embodiment 6
CAPG tensio-active agent (CAPG-12143) with 50%, water, Glacial acetic acid, water glass are 0.6: 20: 0.78 by mass ratio: 2.73 mix, 50 ℃ of stirrings, stirred 10 hours, and filtered deionized water rinsing, after 80 ℃ of dryings, roasting is 4 hours in 350 ℃ of air, obtains the white powder product, and productive rate is 90%, can obtain the mesoporous silicon oxide of cube phase, the d value is 8.7nm.
Embodiment 7
CAPG tensio-active agent (CAPG-12143) with 50%, water, Glacial acetic acid, water glass are 1.2: 20: 0.78 by mass ratio: 2.73 mix, 40 ℃ of stirrings, stirred 10 hours, and filtered deionized water rinsing, after 80 ℃ of dry airs, roasting is 4 hours in 350 ℃ of air, obtains the white powder product, and productive rate is 89%, can obtain the mesoporous silicon oxide of cube phase, the d value is 8.3nm.
Embodiment 8
CAPG tensio-active agent (CAPG-08143) with 50%, water, the vitriol oil, water glass are 0.9: 20: 0.87 by mass ratio: 2.78 mix, 19 ℃ of stirrings, stirred 10 hours, and filtered deionized water rinsing, after 80 ℃ of dryings, roasting is 5 hours in 350 ℃ of air, obtains the white powder product, and productive rate is 90%, can obtain the mesoporous silicon oxide of cube phase, the d value is 11.3nm.
Embodiment 9
CAPG tensio-active agent (CAPG-12143) with 50%, water, the vitriol oil, water glass are 0.6: 20: 0.78 by mass ratio: 2.73 mix, 70 ℃ of stirrings, stirred 6 hours, and filtered deionized water rinsing, after 80 ℃ of dry airs, roasting is 3 hours in 500 ℃ of air, obtains the white powder product, and productive rate is 87%, can obtain the mesoporous silicon oxide of cube phase, the d value is 11.6nm.
Embodiment 10
CAPG tensio-active agent (CAPG-08143) with 50%, water, 1M sodium hydroxide solution, tetraethoxy are 0.9: 20: 1.89 by mass ratio: 2 mix, 23 ℃ of stirrings, stirred 20 hours, and filtered deionized water rinsing, after 90 ℃ of dry airs, roasting is 4 hours in 400 ℃ of air, obtains the white powder product, and productive rate is 89%, can obtain the mesoporous silicon oxide of cube phase, the d value is 10.6nm.
Embodiment 11
CAPG tensio-active agent (CAPG-12143) with 50%, water, 1M sodium hydroxide solution, tetraethoxy are 0.6: 20: 1.89 by mass ratio: 2 mix, 50 ℃ of stirrings, stirred 8 hours, and filtered deionized water rinsing, after 80 ℃ of dry airs, roasting is 4 hours in 500 ℃ of air, obtains the white powder product, and productive rate is 87%, can obtain the mesoporous silicon oxide of cube phase, the d value is 9.8nm.
Embodiment 12
CAPG tensio-active agent (CAPG-12143) with 50%, water, 1M sodium hydroxide solution, tetraethoxy are 1.2: 20: 1.89 by mass ratio: 2 mix, 13 ℃ of stirrings, stirred 15 hours, and filtered deionized water rinsing, after 50 ℃ of dry airs, roasting is 4 hours in 550 ℃ of air, obtains the white powder product, and productive rate is 88%, can obtain the mesoporous silicon oxide of cube phase, the d value is 10.4nm.
Claims (5)
1. one kind is the synthesizing ordered mesoporous SiO of template with the CAPG
2The method of material, concrete steps are as follows:
1) be 0.4～4: 10～50 with mass ratio, at first: mix in 0.5～2: 1～4 the CAPG aqueous solution, water, alkali or acid, silicon source, stirs down at 10～70 ℃; The mass percent concentration of the described CAPG aqueous solution is 50%;
2), filter then, wash, drying, and, obtain the cubic mesoporous earth silicon material of d value at 2～14nm 350 ℃～550 ℃ roastings.
2. according to the synthetic method described in the claim 1, it is characterized in that: described silicon source is a kind of in tetraethoxy or the water glass.
3. according to the synthetic method described in the claim 1, it is characterized in that: used alkali is ammoniacal liquor or sodium hydroxide solution, and acid is acetic acid or sulfuric acid.
4. according to the synthetic method described in the claim 1, it is characterized in that: described 1) churning time in the step is 4～24 hours.
5. according to the synthetic method described in the claim 1, it is characterized in that: described 2) drying temperature in the step is 25～100 ℃.
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| CN108276459A (en) * | 2018-01-08 | 2018-07-13 | 扬州工业职业技术学院 | A kind of NAPG-SiO2Nano material and its application as oil-spill dispersant |
| CN108165245A (en) * | 2018-01-08 | 2018-06-15 | 扬州工业职业技术学院 | A kind of preparation method of silicon dioxide carried cationic alkyl glycosides type pour point depressant for crude oil |
| CN108554310A (en) * | 2018-01-08 | 2018-09-21 | 扬州工业职业技术学院 | A kind of preparation method of silicon dioxide carried polyethers amido alkyl glycosides type oil-spill dispersant |
| CN110203938A (en) * | 2019-06-10 | 2019-09-06 | 蚌埠学院 | A kind of method and its application preparing multi-stage porous silicon dioxide ultrafine powder body for template based on glucan |
| CN111850236A (en) * | 2020-07-23 | 2020-10-30 | 芜湖县天海耐火炉料有限公司 | Covering agent for steelmaking and preparation method thereof |
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| CN1342607A (en) * | 2001-08-24 | 2002-04-03 | 复旦大学 | Process for synthesizing mesoporous SiO2 melecular sieve with cubic structure |
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| CN1342607A (en) * | 2001-08-24 | 2002-04-03 | 复旦大学 | Process for synthesizing mesoporous SiO2 melecular sieve with cubic structure |
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