CN1211277C - Mesoporous silica molecular sieve with large 3D cubic hole hollow structure and its synthesis process - Google Patents
Mesoporous silica molecular sieve with large 3D cubic hole hollow structure and its synthesis process Download PDFInfo
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- CN1211277C CN1211277C CN 01126992 CN01126992A CN1211277C CN 1211277 C CN1211277 C CN 1211277C CN 01126992 CN01126992 CN 01126992 CN 01126992 A CN01126992 A CN 01126992A CN 1211277 C CN1211277 C CN 1211277C
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- molecular sieve
- synthetic method
- hollow structure
- silicon source
- mesoporous silica
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Abstract
The present invention relates to a novel meson-porous silicon dioxide molecular sieve with large pore diameters and three-dimensional cubic pore hollow structure and a synthesizing method thereof. The molecular sieve is prepared by the method that an amphiphilic non-ionic block polymer surfactant, water, acid and a silicon source are mixed, and after being stirred for a period of time at room temperature, the products are filtered, washed by water, dried in the air and roasted at high temperature to obtain the molecular sieve. The meson-porous molecular sieve synthesized by the method has novel three-dimensional cubic pore hollow structure (the space group is Im*m) and has the characteristics of large specific surface area, large and uniform pore size distribution, etc. The meson-porous molecular sieve can be widely used for catalysis, adsorption, separation and preparation of sensors, miniature elements, optical, electric and magnetic functional materials, etc.
Description
Technical field
The invention belongs to the inorganic porous material technical field, be specifically related to a kind of silica mesoporous zeolite and synthetic method thereof, particularly a kind of large 3 D cubic hole hollow structure (spacer Im 3m) mesoporous silica molecular sieve and synthetic method thereof.
Technical background
Mesopore molecular sieve be meant with the tensio-active agent be the class aperture that under the colloidal sol-gelation process of certain condition, assembles of supramolecule template by inorganic species between 2～50nm, the inorganic porous material of compound with regular structure.Compare with traditional micro porous molecular sieve, arrange characteristics such as long-range order, specific surface height, good relatively thermostability and hydrothermal stability, be subjected to scientist's extensive concern because it has meticulous adjustable, the duct in big and pore size distribution, the aperture of homogeneous.Utilize its special performances, people to its absorption with separate, the assembling of functional materialss such as catalyzer and carrier, light, electricity, magnetic, the Application Areass such as preparation of nano material launched extensive studies.
Scientist by U.S. Mobil company synthesizes the MCM-41 (p6mm) that M41S series Jie mesoporous silicon aluminate molecular screen material M41S comprises hexagonal structure the earliest, the MCM-50 of MCM-48 of cubic structure (Ia3d) and laminate structure (L α), they are to adopt cats product alkyl trimethyl ammonium to be synthesized into as template direct hydro-thermal under alkaline condition.Other texture ratio is clearer and more definite also comprises SBA series mesoporous molecular sieve, as SBA-1 (Pm3n); SBA-2, SBA-12 (P6
3/ mmc); SBA-8 (cmm); SBA-11 (Pm3m); SBA-3, SBA-15 (p6m) and SBA-16 (Im 3m) etc.When wherein using polyethylene oxide-poly(propylene oxide)-polyethylene oxide triblock copolymer (EO-PPO-EO), can synthesize, but pore size has the SBA-15 of high-sequential one-dimensional channels and hydrothermally stable at 4.6～30nm modulation as structure directing agent; When use has big EO segmental segmented copolymer, also can synthesize the SBA-16 of cube cage structure.The mesopore molecular sieve of cube phase structure because it has three-dimensional open-framework, catalysis with applications such as separate in better material transfer performance is arranged, than mesoporous material more applications value is arranged with one-dimensional channels two dimension hexagonal meso-hole structure.
The mesopore molecular sieve of present cube phase structure mainly comprises: the SBA-1 of simple cubic structure (Pm3n), SBA-11 (Pm3m); The MCM-48 of body-centered cubic structure (Ia3d), SBA-16 (Im 3m).But their aperture all is lower than 6nm, has limited it to a certain extent in bulky molecular catalysis and the application that separates.
Summary of the invention
The object of the invention is to solve the less limitation in aperture that present three-dimensional cubic structure mesoporous material exists, and a kind of mesoporous silica molecular sieve material and synthetic method thereof with large 3 D cubic hole hollow structure is provided.
The mesoporous silica molecular sieve that the present invention proposes has hole, three-dimensional cubic hole, wide aperture meso-hole structure, spacer is Im 3m, three-dimensional open-framework high-sequential, its aperture are far longer than the mesopore molecular sieve of general cube phase structure, are up to 20nm.
The invention allows for the synthetic method of mesoporous silica molecular sieve with large 3 D cubic hole hollow structure, it is a structure directing agent with amphiphilic nonionic block macromolecular tensio-active agent, under acidic conditions, the hydrolysis of silicon source is obtained, concrete steps are as follows: at first be that amphiphilic nonionic block macromolecular, water, acid and silicon source are mixed by certain molar ratio as (0.01-0.05): (400-800): (4-6): (3.0-5.0) mix, stir for some time down at 0～60 ℃, form organic-inorganic composite body; Passed through again hydrothermal treatment consists 20-120 hour, and filtered then, washing, air be dry down, and form in 450-550 ℃ of roasting.
In the technique scheme amphiphilic nonionic block macromolecular tensio-active agent can adopt polyethylene oxide-polybutylene oxide-polyethylene oxide triblock copolymer (as B50-6600, EO
39-BO
47-EO
39, molecular weight 6800).Organosilicon can be adopted in the silicon source, a kind of as methyl silicate, tetraethoxy, positive silicic acid propyl ester and butyl silicate; Inorganic silicon also can be adopted in the silicon source, a kind of as water glass, water glass and silicon sol.In the aforesaid method, acid can be adopted HCl, H
2SO
4, HNO
3And H
3PO
4A kind of.
The silica mesoporous zeolite with three-dimensional cubic structure (Im 3m) that the present invention synthesizes is designated as FDU-1, and its unit cell parameters reaches 22.0nm, specific surface area Da Gaokeda 1000m
2/ g, pore volume are 0.77～1.5cm
3/ g.Product detects through XRD determining and TEM, confirms as to have the mesoporous silica molecular sieve that spacer is Im 3m.Aperture, specific surface area and pore volume can be by block macromolecular molecular weight or add organic expander such as 1, dimethyl benzene, toluene, benzene and hexanaphthene wait and regulate, its pore diameter range is 3.4-20.0nm.The molecular sieve of the present invention preparation is in bulky molecular catalysis, absorption and separate, be widely used in the preparation of functional materialss such as transmitter, micro element and light, electricity, magnetic.
Embodiment:
The invention will be further elaborated below by embodiment:
Under 1,25 ℃ of the embodiment, with 5.0g EO
39-BO
47-EO
39Be dissolved in 300g 0.5MolL
-1Hydrochloric acid soln, the back that stirs adds 20.8g tetraethoxy (TEOS), EO
39-BO
47-EO
39, water, HCl and tetraethoxy mol ratio be 0.007: 166.7: 1.5: 1.After the continuously stirring 24 hours, hydrothermal treatment consists after 24 hours is filtered mixture, deionized water rinsing, after the vacuum-drying in 500 ℃ of following roastings 4 hours.
The main physico-chemical property of product: specific surface area 740m
2/ g, aperture 12.0nm, pore volume 0.77cm
3/ g, unit cell parameters 17.1nm.
Under 2,25 ℃ of the embodiment, with 5.0g EO
39-BO
47-EO
39Be dissolved in 300g 2.0MolL
-1Hydrochloric acid soln, the back that stirs adds 20.8g tetraethoxy (TEOS), EO
39-BO
47-EO
39, water, HCl and tetraethoxy mol ratio be 0.007: 166.7: 6.0: 1.After the continuously stirring 24 hours, hydrothermal treatment consists after 50 hours is filtered mixture, deionized water rinsing, after the vacuum-drying in 500 ℃ of following roastings 4 hours.
The main physico-chemical property of product: specific surface area 740m
2/ g, aperture 12.0nm, pore volume 0.77cm
3/ g, unit cell parameters 17.1nm.
Under 3,25 ℃ of the embodiment, with 3.0g EO
39-BO
47-EO
39With 1.5g 1,3, the 5-trimethylbenzene is dissolved in 300g 0.5MolL
-1Hydrochloric acid soln, the back that stirs adds 20.8g tetraethoxy (TEOS), EO
39-BO
47-EO
39, water, HCl and tetraethoxy mol ratio be 0.004: 166.7: 1.5: 1.After the continuously stirring 60 hours, hydrothermal treatment consists after 24 hours is filtered mixture, deionized water rinsing, after the vacuum-drying in 500 ℃ of following roastings 4 hours.
The main physico-chemical property of product: specific surface area 680m
2/ g, aperture 14.0nm, pore volume 1.2cm
3/ g, unit cell parameters 22.0nm.
Under 4,0 ℃ of the embodiment, with 5g EO
39-BO
47-EO
39Be dissolved in 300g 0.5MolL
-1Hydrochloric acid soln, the back that stirs adds 20.8g tetraethoxy (TEOS), EO
39-BO
47-EO
39, water, HCl and tetraethoxy mol ratio be: 0.007: 166.7: 1.5: 1.After the continuously stirring 24 hours, hydrothermal treatment consists after 100 hours is filtered mixture, deionized water rinsing, after the vacuum-drying in 500 ℃ of following roastings 4 hours.
The main physico-chemical property of product: specific surface area 700m
2/ g, aperture 11.9nm, pore volume 0.69cm
3/ g, unit cell parameters 19.8nm.
Under 5,60 ℃ of the embodiment, with 5g EO
39-BO
47-EO
39Be dissolved in 200g 0.5MolL
-1Hydrochloric acid soln, the back that stirs adds 20.8g tetraethoxy (TEOS), EO
39-BO
47-EO
39, water, HCl and tetraethoxy mol ratio be 0.007: 111: 1.0: 1.After the continuously stirring 24 hours, hydrothermal treatment consists after 24 hours is filtered mixture, deionized water rinsing, after the vacuum-drying in 450 ℃ of following roastings 4 hours.
The main physico-chemical property of product: specific surface area 710m
2/ g, aperture 12.0nm, pore volume 0.71cm
3/ g, unit cell parameters 16.7nm.
Under 6,25 ℃ of the embodiment, with 5g EO
39-BO
47-EO
39Be dissolved in the 240g distilled water, the back adds 28.4g water glass (Na
2SiO
39H
2O), the back that stirs adds 6MolL
-1Hydrochloric acid soln 60g, EO
39-BO
47-EO
39, water, HCl and water glass (Na
2SiO
39H
2O) mol ratio is 0.007: 175: 3.6: 1.After the continuously stirring 24 hours, hydrothermal treatment consists after 30 hours is filtered mixture, deionized water rinsing, after the vacuum-drying in 550 ℃ of following roastings 4 hours.
The main physico-chemical property of product: specific surface area 510m
2/ g, aperture 10.7nm, pore volume 0.61cm
3/ g, unit cell parameters 15.7nm.
Claims (7)
1, a kind of mesoporous silica molecular sieve, the aperture that it is characterized in that having spacer and be Im 3m reaches hole, 10.7--20nm three-dimensional cubic hole meso-hole structure.
2, a kind of synthetic method of mesoporous silica molecular sieve of large 3 D cubic hole hollow structure as claimed in claim 1, it is characterized in that with amphiphilic nonionic block macromolecular tensio-active agent be structure directing agent, under acidic conditions, the hydrolysis of silicon source is obtained, concrete steps are as follows: be (0.01-0.05) in molar ratio with amphiphilic nonionic block macromolecular tensio-active agent, water, acid, silicon source at first: (400-800): (15-25): (3.0-5.0) mix, stir down at 0～60 ℃, form organic-inorganic composite body; Hydrothermal treatment consists 20-120 hour then, form again through dry under filtration, washing, the air, and in 450～550 ℃ of roastings.
3, synthetic method according to claim 2 is characterized in that amphiphilic nonionic block macromolecular is polyethylene oxide-polybutylene oxide-polyethylene oxide triblock copolymer.
4, synthetic method according to claim 2 is characterized in that a kind of of silicon source employing methyl silicate, tetraethoxy, positive silicic acid propyl ester and butyl silicate.
5, synthetic method according to claim 2 is characterized in that a kind of of the employing of silicon source water glass, silicon sol or water glass.
6, synthetic method according to claim 2 is characterized in that used acid is HCl, H
2SO
4, HNO
3And H
3PO
4A kind of.
7, synthetic method according to claim 2 is characterized in that also adding a kind of of organic expander 1, dimethyl benzene, toluene, benzene and hexanaphthene.
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|---|---|---|---|
| CN 01126992 CN1211277C (en) | 2001-10-11 | 2001-10-11 | Mesoporous silica molecular sieve with large 3D cubic hole hollow structure and its synthesis process |
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|---|---|---|---|
| CN 01126992 CN1211277C (en) | 2001-10-11 | 2001-10-11 | Mesoporous silica molecular sieve with large 3D cubic hole hollow structure and its synthesis process |
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| CN1211277C true CN1211277C (en) | 2005-07-20 |
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| EP2768772A1 (en) * | 2011-11-23 | 2014-08-27 | Dow Global Technologies LLC | High porosity mesoporous siliceous structures |
| JP2014533653A (en) * | 2011-11-23 | 2014-12-15 | ダウ グローバル テクノロジーズ エルエルシー | An environmentally friendly method of preparing mesoporous silica structures |
| CN107236398B (en) * | 2017-07-20 | 2019-09-06 | 广西师范学院 | Imitative stone dumb light sliver paint and preparation method thereof for construction exterior paint |
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