CN1274593C - Preparation method of silicon oxide uniwafer material with ordered hole - Google Patents
Preparation method of silicon oxide uniwafer material with ordered hole Download PDFInfo
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- CN1274593C CN1274593C CN 200310108844 CN200310108844A CN1274593C CN 1274593 C CN1274593 C CN 1274593C CN 200310108844 CN200310108844 CN 200310108844 CN 200310108844 A CN200310108844 A CN 200310108844A CN 1274593 C CN1274593 C CN 1274593C
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Abstract
The present invention relates to a method for quickly preparing large sized, flawless and ordered mesoporous silica single chip material. The present invention improves the traditional sol-gel method, introduces inert medium liquid as a pattern protective agent, realizes solvent evaporation at high temperature, and prepares large sized, complete, transparent, flawless and ordered mesoporous silica single chip material at a short time. The material has high ordered hexagonal or cubic mesoscopic structure. The pore diameter is from 3 to 15 nm, the pore volume is from 0.4 to 1.2cm<3>/g, the ratio surface is from 400 to 700 m<2>/g, and the transmissivity of visual light is equivalent to that of optical glass with an equal thickness. The present invention has the advantages of short synthesis period, simple procedure and easy control, and thus, the present invention enables mesoporous single chip material to be practically applied to catalysis, separation, optical material, etc.
Description
Technical field
The invention belongs to the meso pore silicon oxide material technical field, be specifically related to the fast preparation method of a kind of large size, fissureless mesopore silicon oxide single piece of material.
Background technology
Inorganic single piece of material with the sol-gel process preparation has huge potential using value at optical field, and this type of material transmittance height easily carries out chemical doping and modification, can be used as camera lens, monochromator, nonlinear optical medium etc.Mesopore molecular sieve has the pore passage structure of high-sequential, and high specific surface area and good thermostability are at catalysis, separation, optical material with aspect the synthesizing ordered nanostructure of hard template important Practical significance is arranged.And mesoporous single piece of material is except these characteristics, also has very little outer surface area, height-oriented property and successive pore passage structure on a large scale, and therefore more considerable prospects for commercial application is arranged.At present, the synthesizing mesoporous silicon dioxide single piece of material is solvent evaporation method or the microemulsion method preparation under inducing by segmented copolymer.In order to eliminate the cracked phenomenon of single piece of material in preparation process, supercritical extraction, sealed penetration drying or vacuum drying method have generally been adopted.These methods are generally to the equipment requirements harshness, and required time is grown (8-12 week) very much, very are unfavorable for the suitability for industrialized production of this type of material, are difficult to obtain the single piece of material of fissureless mesopore silicon oxide.We find that under study for action by introducing inert media as the pattern protective material, related volatilization process can carry out during material was synthetic, thereby obtained large size, fissureless ordered meso-porous silicon oxide single piece of material within a short period of time under comparatively high temps.
Summary of the invention
The objective of the invention is to, propose a kind of method for preparing large size, fissureless ordered meso-porous silicon oxide single piece of material quickly and easily,, reduce preparation cost so that shorten preparation time.
The method for preparing large size, fissureless ordered meso-porous silicon oxide single piece of material proposed by the invention is to introduce inert media as the pattern protective material, is covered in gel surface with secluding air; Thermostatically heating under comparatively high temps makes solvent quicken volatilization simultaneously.Concrete steps are as follows: at first tensio-active agent is dissolved in the acidic solution, waits to dissolve the back and add the silicon source, the mass ratio of its initial reactant is tensio-active agent: C
2H
5OH: TEOS: H
2O: HCl=1: (4-6): (1.16-3.47): (0-0.8): (0.007-0.056).Wherein, C
2H
5OH is an etoh solvent, and TEOS is a silicon source tetraethoxy.Leaving standstill under room temperature after stirring made it fully aging in 16-72 hour.Then the gained gel surface cover a layer thickness be the inert media of 2-8mm with secluding air, and, form the meso-hole structure organic-inorganic nanocomposite of high-sequential at 40-120 ℃ of following thermostatically heating 6-32 hour; This material heats up through slow, and after tensio-active agent is removed in 350-650 ℃ of high-temperature roasting, forms the single piece of material of mesopore silicon oxide.
The method that the present invention proposes, the inert media of employing are high boiling point, with silicon oxide and tensio-active agent chemical reaction and immiscible fluent meterial do not take place.Generally select whiteruss, silicone oil etc. for use, also can select for use other to meet the inert media of above-mentioned requirements.
The auxiliary heat time of inert media of the present invention is 6-32 hour, and the synthesis cycle of single piece of material is 1-5 days, well below the use perforation method synthetic 8-12 week of routine.
The method that the present invention proposes can be adjusted the final shape and size of monolithic by the shape of change container and the consumption of reactant.The gained scantling is 0.5 * 0.5 * 0.2cm～10.0 * 10.0 * 1.2cm.
The method that the present invention proposes, it is 400-700m that the meso pore silicon oxide material of institute's synthetic high-sequential has big specific surface area
2/ g and big aperture 3-15nm.
The method that the present invention proposes, institute's synthetic meso pore silicon oxide material has the mesoscopic structure of high-sequential, is generally two-dimentional hexagonal structure (spacer is p6mm) and three-dimensional cubic structure (spacer is Ia3d or Im3m).
The method that the present invention proposes, the tensio-active agent that uses can be cats product, nonionic surface active agent and other high-molecular copolymers.
The method that the present invention proposes, institute's synthetic has the compound single piece of material leakless of organic and inorganic of the meso-hole structure of high-sequential, and is suitable to the opticglass of the transmitance of visible light (optical wavelength 450-850nm) and same thickness.
The method that the present invention proposes, the inert media that is adopted, general through being covered in after fully aging on the gel with secluding air, its thickness is decided on the size of required preparation single piece of material, is generally 2-8mm.If select the lower inert media of density for use, also can be covered on the colloidal sol when aging forming colloidal sol.
The method that the present invention proposes can be regulated the aperture and the pore passage structure of gained mesoporous material by the reconciliation statement surface-active agent.
The method that the present invention proposes can be by metal-salt (as CoCl
36H
2O, FeCl
36H
2O, CuSO
46H
2O etc.) adding is mixed, and realizes the regulation and control to optical property.
The method that the present invention proposes, single piece of material that not only can synthesizing mesoporous monox is suitable for synthetic other mesoporous single piece of material equally, as titanium oxide, titanium phosphate or the like.
The present invention greatly reduces the synthetic difficulty of large size, leakless ordered meso-porous silicon oxide single piece of material, and the compound single piece of material regular shape of the metastructure organic-inorganic nano that contains tensio-active agent that makes is very transparent, is suitable for making optical material; Removing the mesoporous single piece of material that tensio-active agent obtains is having a wide range of applications aspect catalysis, the separation.
Embodiment
Embodiment 1,1 gram Pluronic 123 (P123, EO
20PO
70EO
20) be dissolved in the solution of 5 gram ethanol and 0.2 gram 1mol/L hydrochloric acid composition, stir and make its dissolving, add 2.08 gram TEOS then, continued stir about 10 minutes.Colloidal sol is moved in the container with definite shape (generally selecting porcelain crucible for use), leave standstill for some time (the concrete time decides on temperature, humidity and ventilation situation at that time, is generally 20-48 hour) and make it fully aging.On gel, cover one deck whiteruss then and place oil bath to take out after 24 hours, promptly obtain monolithic after wiping surface liquid paraffin with 60 ℃ of heating.Then 0.5 degree/minute speed be warming up to 550 ℃ and roasting 6 hours to remove tensio-active agent fully, obtain the mesoporous single piece of material of high-sequential.Through PXRD, BET, TEM etc. analyze test shows, and gained is high-quality two-dimentional hexagonal structure (spacer is a p6mm) silicon oxide single piece of material, and its specific surface area is 640m
2/ g, the aperture is 5.65nm, pore volume is 0.93cm
3/ g.
Embodiment 2,1 gram Pluronic 123 (P123, EO
20PO
70EO
20) be dissolved in the solution of 5 gram ethanol and 0.2 gram 1mol/L hydrochloric acid composition, stir and make its dissolving, add 2.08 gram TEOS then, continued stir about 10 minutes.Colloidal sol is moved in the container with definite shape (generally selecting porcelain crucible for use), leave standstill for some time (the concrete time decides on temperature, humidity and ventilation situation at that time, is generally 20-48 hour) and make it fully aging.On gel, cover one deck whiteruss then and place oil bath to take out after 8-24 hour, promptly obtain monolithic after wiping surface liquid paraffin with 90 ℃ of heating.Then 0.5 degree/minute speed be warming up to 550 ℃ and roasting 6 hours to remove tensio-active agent fully, obtain the mesoporous single piece of material of high-sequential.Through PXRD, BET, TEM etc. analyze test shows, and gained is high-quality three-dimensional cubic structure (spacer is an Ia3d) silicon oxide single piece of material, and its specific surface area is 450m
2/ g, the aperture is 5.15nm, pore volume is 0.67cm
3/ g.
Embodiment 3,0.6 gram Brij 97 are dissolved in the solution of 5 gram ethanol and 0.2 gram 1mol/L hydrochloric acid composition, stir and make its dissolving, add 2.08 gram TEOS then, continue stir about 10 minutes.Colloidal sol is moved in the container with definite shape (generally selecting porcelain crucible for use), leave standstill for some time (the concrete time decides on temperature, humidity and ventilation situation at that time, is generally 20-48 hour) and make it fully aging.On gel, cover one deck whiteruss then and place oil bath to take out after 24 hours, promptly obtain monolithic after wiping surface liquid paraffin with 60 ℃ of heating.Then 0.5 degree/minute speed be warming up to 550 ℃ and roasting 6 hours to remove tensio-active agent fully, obtain the mesoporous single piece of material of high-sequential.Through PXRD, BET, TEM etc. analyze test shows, and gained is high-quality two-dimentional hexagonal structure (spacer is a p6mm) silicon oxide single piece of material, and its specific surface area is 440m
2/ g, the aperture is 3.20nm, pore volume is 0.63cm
3/ g.
Embodiment 4,0.8 gram F127 are dissolved in the solution of 5 gram ethanol and 0.2 gram 1mol/L hydrochloric acid composition, stir and make its dissolving, add 2.08 gram TEOS then, continue stir about 10 minutes.Colloidal sol is moved in the container with definite shape (generally selecting porcelain crucible for use), leave standstill for some time (the concrete time decides on temperature, humidity and ventilation situation at that time, is generally 20-48 hour) and make it fully aging.On gel, cover one deck whiteruss then and place oil bath to take out after 24 hours, promptly obtain monolithic after wiping surface liquid paraffin with 60 ℃ of heating.Then 0.5 degree/minute speed be warming up to 550 ℃ and roasting 6 hours to remove tensio-active agent fully, obtain the mesoporous single piece of material of high-sequential.Through PXRD, BET, TEM etc. analyze test shows, and gained is high-quality body-centered cubic structure (spacer is an Im3m) silicon oxide single piece of material, and its specific surface area is 423m
2/ g, the aperture is 8.1nm, pore volume is 0.89cm
3/ g.
Claims (2)
1, a kind of preparation method of ordered meso-porous silicon oxide single piece of material is characterized in that concrete steps are as follows: at first tensio-active agent is dissolved in the acidic solution, waits to dissolve the back and add the silicon source, the mass ratio of its initial reactant is tensio-active agent: C
2H
5OH: TEOS: H
2O: HCl=1: (4-6): (1.16-3.47): (0-0.8): (0.007-0.056); Under room temperature, left standstill 16-72 hour after stirring, make it fully aging; The inert media that covers one deck 2-8mm in the gained gel surface is with secluding air then, and at 40-120 ℃ of following thermostatically heating 6-32 hour, forms the meso-hole structure organic-inorganic nanocomposite of high-sequential; This material is slowly heated up, remove tensio-active agent, form the single piece of material of mesopore silicon oxide in 350-650 ℃ of high-temperature roasting; Wherein, inert media is whiteruss or silicone oil, and tensio-active agent is P123, Brij97, F127.
2, according to the preparation method of claim 1, it is characterized in that: adjust the final shape and size of monolithic by the shape of change container and the consumption of reactant, the gained scantling is 0.5 * 0.5 * 0.2cm～10.0 * 10.0 * 1.2cm.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200310108844 CN1274593C (en) | 2003-11-25 | 2003-11-25 | Preparation method of silicon oxide uniwafer material with ordered hole |
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|---|---|---|---|
| CN 200310108844 CN1274593C (en) | 2003-11-25 | 2003-11-25 | Preparation method of silicon oxide uniwafer material with ordered hole |
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| CN1274593C true CN1274593C (en) | 2006-09-13 |
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Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101081699B (en) * | 2006-05-31 | 2010-04-14 | 南京理工大学 | Ordered meso-porous silicon oxide and rapid preparation method thereof |
| CN101266378B (en) * | 2007-12-28 | 2014-04-02 | 中国科学院上海硅酸盐研究所 | Organic-inorganic composite non-linear optical film and method for making same |
| CN101289192B (en) * | 2008-06-05 | 2010-06-02 | 太原理工大学 | Method for preparing transparent meso-porousearth silicon gel monolithi material |
| US11490846B2 (en) | 2016-06-30 | 2022-11-08 | Tatsuta Electric Wire & Cable Co., Ltd. | Bioelectrode and method for producing bioelectrode |
| CN113769703B (en) * | 2021-08-20 | 2024-07-12 | 绍兴蓝竹新材料科技有限公司 | Preparation method of amino-functionalized ordered mesoporous silica adsorbent |
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