CN1169716C - SiO2 molecular sieve with 3D pore canal and 2D mesopore structure and its synthesizing process - Google Patents
SiO2 molecular sieve with 3D pore canal and 2D mesopore structure and its synthesizing process Download PDFInfo
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- CN1169716C CN1169716C CNB011268808A CN01126880A CN1169716C CN 1169716 C CN1169716 C CN 1169716C CN B011268808 A CNB011268808 A CN B011268808A CN 01126880 A CN01126880 A CN 01126880A CN 1169716 C CN1169716 C CN 1169716C
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Abstract
The present invention relates to a novel silicon oxide molecular sieve with three-dimensional pore canals in a two dimensional mesoporous structure and a synthetic method thereof. The silicon oxide molecular sieve is formed by that an organic inorganic compound is obtained by mixing and stirring an amphiphilic nonionic block macromolecular surface active agent, water, acids and a silicon source for a peroid of time; then the organic inorganic compound is processed by high temperature hypothermal treatment, filtration, water washing, drying in the air and roasting. The molecular sieve synthesized with the method is in an average two-dimensional hexagonal mesoporous structure, and mesoporous pore canals hexagonally arrayed are mutually connected with 3 to 8 nm mosoporous tunnels so that the novel silicon oxide molecular sieve with pore canals in a three-dimensional structure, a high pore volume and mesopores in a highly ordered two-dimensional structure is formed. The molecular sieve has wide applications in the preparation of macromolecule catalysis, adsorption and separation, sensors, micro devices and functional materials, such as light functional materials, electricity functional materials, magnetism functional materials, etc.
Description
Technical field:
The invention belongs to the inorganic porous material technical field, be specifically related to the SiO 2 molecular sieve and the synthetic method thereof of a kind of silica mesoporous zeolite and synthetic method thereof, particularly 3 D pore canal and 2 D mesopore structure (spacer is p6m).
Technical background:
It is the supramolecule template in a class aperture that the colloidal sol-gelation process of certain condition by inorganic species assembles between 2～50nm that mesopore molecular sieve is meant with the tensio-active agent, the inorganic porous material of compound with regular structure.Compare with traditional micro porous molecular sieve, mesopore molecular sieve has meticulous adjustable, the duct in big and pore size distribution, the aperture of homogeneous and arranges characteristics such as long-range order, specific surface height, good relatively thermostability and hydrothermal stability, thereby is subjected to scientist's extensive concern.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 mesoporous aluminoshilicate 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 chain 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 (p6mm) and SBA-16 (Im 3m) etc.When wherein using polyethylene oxide-poly(propylene oxide)-polyethylene oxide triblock copolymer (EO-PO-EO) as structure directing agent, can synthesize high-sequential, but pore size has the SBA-15 of high-sequential one-dimensional channels and hydrothermally stable at 4.6～30nm modulation.But the one-dimensional channels of SBA-15 has limited the multidimensional transmission of material to a certain extent.
Summary of the invention:
The object of the invention is to solve the limitation that present SBA-15 mesoporous material exists, and a kind of mesoporous silica molecular sieve and synthetic method thereof with 3 D pore canal and 2 D mesopore structure (spacer is p6m) is provided.
The SiO 2 molecular sieve of the 3 D pore canal and 2 D mesopore structure that the present invention proposes, not only has orderly 2 D mesopore structure, and interconnect by the mesoporous tunnel of 3～8nm between the mesopore orbit arranged of hexagonal, form a kind of novel three-dimensional pore passage structure, high pore volume, high-sequential 2 D mesopore structure silica material.
The invention allows for the synthetic method of above-mentioned 3 D pore canal and 2 D mesopore structure SiO 2 molecular sieve, 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 tensio-active agent, water, acid and silicon source are (0.02-0.10) in molar ratio: (400-800): (15-25): (3.0-5.0) mix, stir down at 15～80 ℃, form organic-inorganic composite body, under 120～150 ℃ of high temperature, carry out hydrothermal treatment consists then, washing more after filtration,, air descend drying, and form 450～600 ℃ of roastings.
In the aforesaid method, adopt polyethylene oxide-poly(propylene oxide)-polyethylene oxide triblock copolymer (EO with amphiphilic nonionic block macromolecular tensio-active agent
20PO
70EO
20) be structure directing agent.Organosilicon source or inorganic silicon source can be adopted in the silicon source, and a kind of of methyl silicate, tetraethoxy, positive silicic acid propyl ester and butyl silicate can be selected in the organosilicon source; The a kind of of water glass and silicon sol can be selected in the inorganic silicon source.
In the aforesaid method, acid can be adopted HCl, H
2SO
4, HNO
3And H
3PO
4A kind of.
Can also add a kind of of organic cosolvent 1, dimethyl benzene, toluene, benzene, n-hexyl alcohol and normal hexane in the aforesaid method, to regulate mesoporous tunnel size.
The mesoporous silica molecular sieve that the present invention synthesizes with 3 D pore canal and 2 D mesopore structure (spacer is p6m), unit cell parameters reaches 10～13nm, and specific surface area reaches 250～700m
2/ g, pore volume are 1.0～1.5cm
3/ g.Resulting product is verified as the mesoporous silica molecular sieve of 3 D pore canal and 2 D mesopore structure (spacer is p6m) through XRD and TEM.Mesoporous tunnel size between the mesopore orbit that hexagonal is arranged can be by changing hydrothermal temperature and adding organic cosolvent and regulate and control.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 1,40 ℃ of the embodiment, with 2.0g EO
20PO
70EO
20Be dissolved in the hydrochloric acid soln of 75g 1.6M, the back that stirs adds the 4.16g tetraethoxy.EO
20PO
70EO
20, water, HCl and tetraethoxy mol ratio be 0.017: 195: 6.0: 1.After the continuously stirring 24 hours, then 130 ℃ of hydrothermal treatment consists 24 hours.Mixture is filtered, deionized water rinsing, after the vacuum-drying in 500 ℃ of following roastings 4 hours.
The main physico-chemical property of product: specific surface area 417m
2/ g, pore volume 1.11cm
3/ g, aperture 10.7nm, unit cell parameters 10.4nm.
Under 2,35 ℃ of the embodiment, with 2.0g EO
20PO
70EO
20Be dissolved in the salpeter solution of 90g 1.6M, the back that stirs adds the 4.16g tetraethoxy.EO
20PO
70EO
20, water, nitric acid and tetraethoxy mol ratio be 0.017: 234: 7.2: 1.Continuously stirring adds the 2g 1 after 65 minutes, continue to stir 24 hours again.130 ℃ of hydrothermal treatment consists after 24 hours are 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 324m
2/ g, pore volume 1.43cm
3/ g, aperture 17.6nm, unit cell parameters 13.0nm.
Under 3,40 ℃ of the embodiment, with 1.6g EO
20PO
70EO
20Be dissolved in the hydrochloric acid soln of 75g 1.6M, the back that stirs adds the 4.16g tetraethoxy.EO
20PO
70EO
20, water, HCl and tetraethoxy mol ratio be 0.014: 195: 6.0: 1.Continuously stirring adds the 2g 1 after 65 minutes, continue to stir 24 hours again.140 ℃ of hydrothermal treatment consists after 24 hours are filtered mixture, deionized water rinsing, after the vacuum-drying in 550 ℃ of following roastings 3 hours.
The main physico-chemical property of product: specific surface area 254m
2/ g, pore volume 1.25cm
3/ g, aperture 22.3nm, unit cell parameters 13.0nm.
Under 4,40 ℃ of the embodiment, with 2.0g EO
20PO
70EO
20Be dissolved in the hydrochloric acid soln of 75g 1.6M, the back that stirs adds the 4.16g tetraethoxy.EO
20PO
70EO
20, water, HCl and tetraethoxy mol ratio be 0.017: 195: 6.0: 1.Continuously stirring adds the 2g 1 after 65 minutes, continue to stir 24 hours again.120 ℃ of hydrothermal treatment consists after 24 hours are 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 538m
2/ g, pore volume 1.40cm
3/ g, aperture 12.7nm, unit cell parameters 12.5nm.
Under 5,40 ℃ of the embodiment, with 2.0g EO
20PO
70EO
20Be dissolved in the sulphuric acid soln of 75g 1.0M, the back that stirs adds 4.16g tetraethoxy (TEOS).EO
20PO
70EO
20, water, sulfuric acid and tetraethoxy mol ratio be 0.017: 195: 7.5: 1.Continuously stirring adds the 2g n-hexyl alcohol after 65 minutes, continue to stir 24 hours again.120 ℃ of hydrothermal treatment consists after 24 hours are filtered mixture, deionized water rinsing, after the vacuum-drying in 600 ℃ of following roastings 3 hours.
The main physico-chemical property of product: specific surface area 653m
2/ g, pore volume 1.36cm
3/ g, aperture 10.6nm, unit cell parameters 10.4nm.
Claims (6)
1, a kind of SiO 2 molecular sieve of 3 D pore canal and 2 D mesopore structure is characterized in that having orderly 2 D mesopore structure, and the mesoporous tunnel by 3～8nm between the mesopore orbit that hexagonal is arranged interconnects.
2, a kind of synthetic method of 3 D pore canal and 2 D mesopore structure SiO 2 molecular sieve, it is characterized in that concrete steps are as follows: at first be that amphiphilic nonionic block macromolecular tensio-active agent, water, acid, silicon source are (0.02-0.10) in molar ratio: (400-800): (15-25): (3.0-5.0) mix, stir down at 15～80 ℃, form organic-inorganic composite body, under 120～150 ℃ of high temperature, carry out hydrothermal treatment consists then, washing more after filtration,, air descend drying, and form 450～600 ℃ of roastings.
3, synthetic method according to claim 2 is characterized in that amphiphilic nonionic block macromolecular tensio-active agent adopts polyethylene oxide-poly(propylene oxide)-polyethylene oxide triblock copolymer as structure directing agent.
4, synthetic method according to claim 2 is characterized in that the silicon source comprises organosilicon source and inorganic silicon source, and the organosilicon source is a kind of of methyl silicate, tetraethoxy, positive silicic acid propyl ester and butyl silicate; The inorganic silicon source is a kind of of water glass or silicon sol.
5,, it is characterized in that to add a kind of of organic cosolvent 1, dimethyl benzene, toluene, benzene, n-hexyl alcohol and normal hexane in the building-up process according to the synthetic method of claim 2.
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.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB011268808A CN1169716C (en) | 2001-09-26 | 2001-09-26 | SiO2 molecular sieve with 3D pore canal and 2D mesopore structure and its synthesizing process |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB011268808A CN1169716C (en) | 2001-09-26 | 2001-09-26 | SiO2 molecular sieve with 3D pore canal and 2D mesopore structure and its synthesizing process |
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| CN1169716C true CN1169716C (en) | 2004-10-06 |
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Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100457618C (en) * | 2002-12-05 | 2009-02-04 | 复旦大学 | Mesoporous material with three-D communicating pore structure and preparing process thereof |
| CN1247455C (en) * | 2002-12-30 | 2006-03-29 | 新加坡纳米材料科技有限公司 | Silicon dioxide mesoporous material and its preparing method |
| CN100419011C (en) * | 2004-11-30 | 2008-09-17 | 财团法人工业技术研究院 | Modified mesoporous silicon dioxide powder, presolution for forming low dielectric opoxy resin and low dielectric polysub amido resin, low dielectric constant base board and its forming method |
| CN101905170B (en) * | 2010-08-16 | 2013-06-12 | 复旦大学 | Preparation method of mesoporous-micropore shell-nuclear structure composite zeolite molecular sieve catalyst |
| CN103987661B (en) * | 2011-11-23 | 2017-02-22 | 陶氏环球技术有限责任公司 | High porosity mesoporous siliceous structures |
| CN102875780B (en) * | 2012-10-17 | 2014-10-15 | 扬州大学 | Preparation method of polytrimethylene terephthalate composite material in-situ synthesized based on mesoporous silica material |
| CN106552609A (en) * | 2016-12-06 | 2017-04-05 | 浙江大学 | Carbon dioxide absorber and its preparation method based on layer stephanoporate silicon dioxide block |
| CN109485060B (en) * | 2017-09-13 | 2020-12-18 | 中国石油化工股份有限公司 | SBA-16 molecular sieve modified by nano iron and preparation method and application thereof |
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2001
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