CN1605562A - Macroporous sillca molecular sieve with ordered three-dimensional interconnected aperture wall and preparation method thereof - Google Patents
Macroporous sillca molecular sieve with ordered three-dimensional interconnected aperture wall and preparation method thereof Download PDFInfo
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- CN1605562A CN1605562A CN 200410054197 CN200410054197A CN1605562A CN 1605562 A CN1605562 A CN 1605562A CN 200410054197 CN200410054197 CN 200410054197 CN 200410054197 A CN200410054197 A CN 200410054197A CN 1605562 A CN1605562 A CN 1605562A
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Abstract
The present invention is macroporous silica molecular sieve material with high ordered 3D communicated mesopore wall and its preparation process. The material is prepared directly through an one-step process with mixed anionic and non-ionic surfactant as structure guiding agent and through forming double-continuous emulsion as template with oil soluble silicon source, mixed surfactant and ion aqua under certain temperature and acidity. Thus synthesized material has 3D communicated macroporous structure and high ordered 3D mesopore structure, two kinds of composite pore sizes, great specific surface area, great pore volume and high heat stability. Compared with traditional method, the present invention has simple preparation process, and the obtained material has good channel communication and thus wide application foreground in separation, catalysis, resisting bacteria, sensor and other fields.
Description
Technical field
The invention belongs to technical field of inorganic material, be specifically related to that a class has the macroporous silica molecular screen material of the mesoporous wall of high-sequential three-dimensional communication and be the preparation method of template with co-continuous milk sap.
Technical background
Compare with other inorganic materials, mesoporous material has big specific surface area and pore volume, evenly adjustable aperture, the surface properties that can modify, controllable pattern and character such as nontoxic, and this has given it and has all had good application prospects in every field such as bio-molecular separation, catalysis, drug molecule and biological enzyme load, transport of substances, chemical sensitisations.Numerous researchists have carried out a large amount of synthetic and applied researcies in this field, the result shows, mesoporous material with three-dimensional communication pore passage structure shows than one-dimensional tunnel structure mesoporous material special advantages more in all many-sides such as drug molecule and biological enzyme load, bio-molecular separation, transport of substances, this mainly is because the former mesopore orbit fully exposes at particle surface and big bore edges, its duct has good connectedness, helps entering and transmitting of target molecule.For this reason, people are exploring to synthesize always has macropore and mesoporous matrix material simultaneously, so that bring into play the advantage of mesoporous material bigger serface and pore volume more fully.
Though more existing in the world at present reports about macroporous/mesoporous matrix material, but they mainly are based on layer laminate (layer-by-layer) technology, the polystyrene latex that utilization has the homogeneous particle diameter is pre-formed the close-packed body, and then in its space, pour into the silicon source precursor that is mixed with tensio-active agent, through hydrolysis and crosslinked, utilize pyroprocessing or solvent-extracted way to remove the polystyrene latex particle at last and make this class material.Because the close-packed body of polystyrene latex particle is difficult to be achieved in the big area scope, this method is not suitable for being used for preparing macroporous/mesoporous matrix material in a large number, thereby has limited the application and the exploitation of mesoporous material.In order to address the above problem, key just is to realize the control of material on macropore and mesoporous two yardsticks, and can find a kind of convenience, cheapness, simple preparation process to synthesize the macroporous/mesoporous matrix material of this class in a large number.
Summary of the invention
The objective of the invention is to propose a kind of have the macroporous silica molecular screen material of the mesoporous wall of high-sequential three-dimensional communication and synthetic method simple and efficient to handle thereof.
It is template that the present invention proposes with co-continuous milk sap, single stage method directly preparation has the method for the macroporous silica molecular screen material of the mesoporous wall of high-sequential three-dimensional communication, the steps include: at first negatively charged ion and nonionic surfactant to be dissolved in the inorganic acid aqueous solution simultaneously, make settled solution.In this solution, add inorganic salt and it is fully dissolved.Stir down, add the oil soluble silicon source of may command hydrolysis again, make it be well dispersed in aqueous phase, and the polycondensation that under this temperature, is hydrolyzed, stop then stirring.System constant temperature leaves standstill for some time, makes oil soluble silicon source, mixed surfactant, salt solution form co-continuous milk sap and produces precipitation by being separated.The gained throw out passes through processing such as hydro-thermal, filtration, washing and drying again, adopts the method for polar organic solvent reflux extraction or high-temperature roasting to remove tensio-active agent at last, promptly obtains having the three-dimensional communication large pore material of highly ordered mesosize pores wall.
Among the above-mentioned preparation method, relevant condition may command is as follows:
Synthesis temperature: 20-50 ℃, churning time: 15-60 minute;
System constant temperature time of repose: 8-24 hour;
The mol ratio of reaction mass is: nonionogenic tenside: anion surfactant: mineral acid: inorganic salt: water=1: (0.8-6): (60-380): (0.8-70): (8600-16500);
The mol ratio of silicon source and total surfactant is 1: (40-90);
Hydrothermal treatment consists temperature: 70-130 ℃; Hydrothermal treatment consists time: 12-72 hour.
Among the present invention, adopt negatively charged ion and nonionic surfactant to synthesize the mesoscopic structure of high-sequential as structure directing agent.The formed micella of mixed surfactant generally has bigger hydrophobic/hydrophilic volume ratio than the micella that single nonionogenic tenside forms, and helps the formation of three-dimensional mesoscopic structure.The anion surfactant that adopts among the present invention can be long chain alkyl sulfates (C
nH
2n+1SO
4M
2), chain alkyl sulfonate (C
nH
2n+1SO
3M), chain alkyl carboxylate salt (C
nH
2n+1COOM) and long-chain alkyl benzene sulfonate (C
nH
2n+1C
6H
4SO
3M), chain alkyl phosphoric acid salt (C
nH
2n+1PO
4M
2), n=8-18, M are Na
+, K
+, NH
4 +Deng.
Among the present invention, adopt inorganic salt to promote the formation of co-continuous milk sap.Because inorganic salt can strengthen the self-assembly ability of mixed surfactant on the one hand, the generation of guiding high quality mesoscopic structure can also reduce the interfacial curvature between oil phase, the water on the other hand, promotes the formation of co-continuous milk sap.The inorganic salt that use among the present invention can be one or more mixtures of sodium sulfate, vitriolate of tartar, ammonium sulfate, sodium pyrosulfate, sal enixum, monoammonium sulfate, SODIUMNITRATE, saltpetre, ammonium nitrate, nitrocalcite, sodium-chlor, Repone K, ammonium chloride, calcium chloride, sodium phosphate, potassiumphosphate, ammonium phosphate, sodium hydrogen phosphate, potassium hydrogen phosphate, ammonium hydrogen phosphate, SODIUM PHOSPHATE, MONOBASIC, potassium primary phosphate, primary ammonium phosphate etc.
Among the present invention, the oil soluble silicon species that adopts the may command hydrolysis is as the silicon source, and it because hydrolysis degree is lower, can be used as the oil phase of co-continuous milk sap in initial reaction stage, and the formation of guiding water-oil interface inorganic silicon dioxide.Along with the raising of its hydrolytie polycondensation degree, the silicon source is gradually to water diffusion, the formation of the three-dimensional macroporous structure that finally leads.Among the present invention, the oil soluble silicon source of the may command hydrolysis of use can be positive quanmethyl silicate, positive tetraethyl orthosilicate, positive silicic acid orthocarbonate, positive silicic acid four isopropyl esters, positive silicic acid four butyl esters or one or more mixture.
Among the present invention, employing has different hydrophilic segmental nonionogenic tenside by controlling Jie's view hole road structure of product with the interworking of anion surfactant, and used nonionogenic tenside is diblock, three block polyox-yethylene-polyoxypropylene block copolymer (C
nH
2n+1EO
m, EO
xPO
yEO
x), include C
12H
25EO
23, C
16H
33EO
10, C
18H
37EO
10, C
16H
33EO
20, C
18H
37EO
20, EO
20PO
70EO
20, EO
17PO
85EO
17, EO
5PO
70EO
5, EO
26PO
39EO
26, EO
20PO
30EO
20, EO
106PO
70EO
106, EO
123PO
47EO
123, EO
132PO
50EO
132Deng.
Among the present invention, the removal of tensio-active agent can be adopted polar organic solvent reflux extraction method, and the solvent of employing has methyl alcohol, ethanol, Virahol, tetrahydrofuran (THF) or their acidic solution; Also can adopt high-temperature roasting method with removal of surfactant, maturing temperature is 400-800 ℃, and the treatment time is 4-10 hour.
The obtained SiO 2 molecular sieve material of the inventive method, this material still can keep mesoscopic structure preferably after 1000 ℃ of thermal treatment 1-5 hours in air, the aperture of handling back gained material is 4.0-8.0nm, pore volume 0.60-1.2cm
3/ g, specific surface area 350-700m
2/ g.
The macroporous silica molecular screen material of the present invention preparation has molecular screen material and has high specific surface area and (be 600-1500m
2/ g) and big pore volume (0.7-1.5cm
3/ g) and good thermostability.
Description of drawings
Fig. 1 uses EO
20PO
70EO
20Make with sodium lauryl sulphate mixed surfactant guiding and compose in the feature XRD figure of 550 ℃ of roastings products therefrom after 5 hours.(its duct spatial symmetry is a cube Ia-3d)
Fig. 2 uses EO
106PO
70EO
106Make with Sodium dodecylbenzene sulfonate mixed surfactant guiding and compose in the feature XRD figure of 500 ℃ of roastings products therefrom after 6 hours.(its duct spatial symmetry is a cube Im-3m)
Fig. 3 is with positive tetraethyl orthosilicate, EO
20PO
70EO
20, sodium lauryl sulphate and the obtained product of aqueous sodium persulfate solution system feature SEM figure.
Embodiment
During 1,30 ℃ of embodiment, with 1.0 gram EO
20PO
70EO
20Be dissolved in the 27 gram water with 0.115 gram sodium lauryl sulphate, add the hydrochloric acid soln and the 0.028 gram anhydrous sodium sulphate of 13 grams, 2.0 mol in the system, stir and make settled solution.Add 2.15 gram tetraethyl orthosilicates under agitation condition, stop after 30 minutes stirring, system left standstill 24 hours in 30 ℃ of constant temperature, and container bottom generates white depositions.This precipitation is transferred in the reactor of tetrafluoroethylene in 100 ℃ of hydro-thermals 24 hours, filtered then, wash and dry, and removed tensio-active agent in 5 hours, promptly obtain macroporous/mesoporous matrix material in 550 ℃ of roastings.The macropore diameter of this material is 4-10 μ m, and mesoporous aperture is 6.5nm, and pore volume is 1.19cm
3/ g, specific surface area is 824m
2/ g, the duct spatial symmetry of material are a cube Ia-3d structure.Its feature XRD figure spectrum is seen shown in Figure 1.
During 2,45 ℃ of embodiment, with 1.0 gram EO
106PO
70EO
106Be dissolved in the 37.5 gram water with 0.084 gram Sodium dodecylbenzene sulfonate, add the hydrochloric acid soln and the 0.186 gram Repone K of 11.5 grams, 2.0 mol in the system, stir and make settled solution.Add 4.8 gram tetraethyl orthosilicates under agitation condition, stop after 20 minutes stirring, system left standstill 20 hours in 45 ℃ of constant temperature, and container bottom generates white depositions.This precipitation is transferred in the reactor of tetrafluoroethylene in 100 ℃ of hydro-thermals 24 hours, filtered then, wash and dry, and removed tensio-active agent in 6 hours, promptly obtain macroporous/mesoporous matrix material in 500 ℃ of roastings.The macropore diameter of this material is 8-20 μ m, and mesoporous aperture is 6.3nm, and pore volume is 1.08cm
3/ g, specific surface area is 816m
2/ g, the duct spatial symmetry of material are a cube Im-3m structure.Its feature XRD figure spectrum is seen shown in Figure 2.
During 3,35 ℃ of embodiment, with 1.0 gram EO
20PO
70EO
20Be dissolved in the 27 gram water with 0.115 gram sodium lauryl sulphate, add the hydrochloric acid soln and the 0.568 gram anhydrous sodium sulphate of 13 grams, 2.0 mol in the system, stir and make settled solution.Add 2.15 gram tetraethyl orthosilicates under agitation condition, stop after 15 minutes stirring, system left standstill 24 hours in 35 ℃ of constant temperature, and container bottom generates white depositions.This precipitation is transferred in the reactor of tetrafluoroethylene in 100 ℃ of hydro-thermals 24 hours, filtered then, wash and dry, and removed tensio-active agent in 5 hours, obtain the macroporous/mesoporous matrix material of coralliform in 550 ℃ of roastings.The macropore diameter of this material is 0.5-4 μ m, and mesoporous aperture is 6.8nm, and pore volume is 1.08cm
3/ g, specific surface area is 798m
2/ g, the duct spatial symmetry of material are a cube Ia-3d structure.Its feature XRD figure spectrum is seen shown in Figure 3.
Claims (10)
1, a kind of macroporous silica molecular screen material is characterized in that: have the macroporous structure of three-dimensional communication on macroscopic view, its inorganic wall that constitutes macropore has orderly three-dimensional meso-hole structure; Its duct spatial symmetry is that its spacer of cubic structure is Ia-3d or Im-3m, perhaps is hexagonal structure, and its spacer is P6
3/ mmc or p6mm; Material has two kinds of composite bore diameters on three-dimensional space: a kind of is macropore, and the aperture is the 0.5-10 micron, and another kind is mesoporous, and the aperture is 4 to 12 nanometers.
2, SiO 2 molecular sieve material according to claim 1, the pore volume that it is characterized in that material is 0.7-1.5cm
3/ g, specific surface area is 600-1500m
2/ g.
3, a kind of preparation method of macroporous silica molecular screen material as claimed in claim 1, it is characterized in that concrete steps are as follows: negatively charged ion and nonionic surfactant are dissolved in simultaneously make settled solution in the inorganic acid aqueous solution earlier, in this solution, add inorganic salt and it is fully dissolved; Stir the oil soluble silicon source that adds the may command hydrolysis down, make it be well dispersed in aqueous phase, and the polycondensation that under this temperature, is hydrolyzed, stop then stirring; System constant temperature leaves standstill for some time, allows and forms co-continuous milk sap between oil soluble silicon source, mixed surfactant, salt solution, and produce precipitation by being separated; Throw out adopts the method for polar organic solvent reflux extraction or high-temperature roasting to remove tensio-active agent through hydro-thermal, filtration, washing and drying treatment at last, promptly obtains having the macroporous silica molecular screen material of the mesoporous wall of high-sequential three-dimensional communication.
4,, it is characterized in that concrete preparation condition is as follows according to the described preparation method of claim 3:
Synthesis temperature: 20-50 ℃, churning time: 15-60 minute;
System constant temperature time of repose: 8-24 hour;
The mol ratio of reaction mass is: nonionogenic tenside: anion surfactant: mineral acid: inorganic salt: water=1: (0.8-6): (60-380): (0.8-70): (8600-16500);
The mol ratio of silicon source and total surfactant is 1: (40-90);
Hydrothermal treatment consists temperature: 70-130 ℃; Hydrothermal treatment consists time: 12-72 hour.
5, preparation method according to claim 3, the oil soluble silicon source that it is characterized in that used may command hydrolysis is one or more a mixture of positive quanmethyl silicate, positive tetraethyl orthosilicate, positive silicic acid orthocarbonate, positive silicic acid four isopropyl esters, positive silicic acid four butyl esters.
6, preparation method according to claim 3, it is characterized in that used inorganic salt are one or more mixture of sodium sulfate, vitriolate of tartar, ammonium sulfate, sodium pyrosulfate, sal enixum, monoammonium sulfate, SODIUMNITRATE, saltpetre, ammonium nitrate, nitrocalcite, sodium-chlor, Repone K, ammonium chloride, calcium chloride, sodium phosphate, potassiumphosphate, ammonium phosphate, sodium hydrogen phosphate, potassium hydrogen phosphate, ammonium hydrogen phosphate, SODIUM PHOSPHATE, MONOBASIC, potassium primary phosphate, primary ammonium phosphate, inorganic salt concentration is the 0.005-0.5 mol.
7, preparation method according to claim 3, it is characterized in that used anion surfactant is long chain alkyl sulfates, chain alkyl sulfonate, chain alkyl carboxylate salt and long-chain alkyl benzene sulfonate, chain alkyl phosphoric acid salt, n=8-18, M are Na
+, K
+, NH
4 +A kind of.
8, preparation method according to claim 3 is characterized in that used nonionogenic tenside is diblock or three block polyox-yethylene-polyoxypropylene block copolymers.
9, preparation method according to claim 3 is characterized in that adopting polar organic solvent reflux extraction method to remove tensio-active agent, and used solvent is methyl alcohol, ethanol, Virahol, tetrahydrofuran (THF) or their acidic solution.
10, preparation method according to claim 3, when it is characterized in that adopting high-temperature roasting method to remove tensio-active agent, maturing temperature is 400-800 ℃, the treatment time is 4-10 hour.
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|---|---|---|---|
| CN 200410054197 CN1291913C (en) | 2004-09-01 | 2004-09-01 | Macroporous sillca molecular sieve with ordered three-dimensional interconnected aperture wall and preparation method thereof |
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|---|---|---|---|
| CN 200410054197 CN1291913C (en) | 2004-09-01 | 2004-09-01 | Macroporous sillca molecular sieve with ordered three-dimensional interconnected aperture wall and preparation method thereof |
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| CN1291913C CN1291913C (en) | 2006-12-27 |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100345597C (en) * | 2005-06-16 | 2007-10-31 | 复旦大学 | Hemostatic material of new type pore-borne molecular sieve and preparation method |
| CN100460321C (en) * | 2005-05-31 | 2009-02-11 | 中国石油化工股份有限公司 | Diplopore silica gel material, and preparation method |
| CN101479044B (en) * | 2006-04-13 | 2012-05-16 | 硅生物系统股份公司 | Method for the selection and/or the processing of particles, in particular cells |
| CN102515172A (en) * | 2011-11-28 | 2012-06-27 | 上海交通大学 | Preparation method of macroporous silica material |
| CN104026737A (en) * | 2014-06-19 | 2014-09-10 | 广西中烟工业有限责任公司 | Harm-reduction type ternary compound filter rod with ordered mesoporous silica particles |
| CN104026736A (en) * | 2014-06-19 | 2014-09-10 | 广西中烟工业有限责任公司 | Harm-reduction type binary compound filter rod with ordered mesoporous silica particles |
| CN107974728A (en) * | 2017-10-25 | 2018-05-01 | 衢州福创工业设计有限公司 | A kind of antibacterial composite high-molecular fiber |
-
2004
- 2004-09-01 CN CN 200410054197 patent/CN1291913C/en not_active Expired - Fee Related
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100460321C (en) * | 2005-05-31 | 2009-02-11 | 中国石油化工股份有限公司 | Diplopore silica gel material, and preparation method |
| CN100345597C (en) * | 2005-06-16 | 2007-10-31 | 复旦大学 | Hemostatic material of new type pore-borne molecular sieve and preparation method |
| CN101479044B (en) * | 2006-04-13 | 2012-05-16 | 硅生物系统股份公司 | Method for the selection and/or the processing of particles, in particular cells |
| CN102515172A (en) * | 2011-11-28 | 2012-06-27 | 上海交通大学 | Preparation method of macroporous silica material |
| CN102515172B (en) * | 2011-11-28 | 2013-09-11 | 上海交通大学 | Preparation method of macroporous silica material |
| CN104026737A (en) * | 2014-06-19 | 2014-09-10 | 广西中烟工业有限责任公司 | Harm-reduction type ternary compound filter rod with ordered mesoporous silica particles |
| CN104026736A (en) * | 2014-06-19 | 2014-09-10 | 广西中烟工业有限责任公司 | Harm-reduction type binary compound filter rod with ordered mesoporous silica particles |
| CN107974728A (en) * | 2017-10-25 | 2018-05-01 | 衢州福创工业设计有限公司 | A kind of antibacterial composite high-molecular fiber |
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| Publication number | Publication date |
|---|---|
| CN1291913C (en) | 2006-12-27 |
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