CN101804989A - Preparation method of transparent mesoporous silica gel monolith - Google Patents
Preparation method of transparent mesoporous silica gel monolith Download PDFInfo
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- CN101804989A CN101804989A CN 201010150341 CN201010150341A CN101804989A CN 101804989 A CN101804989 A CN 101804989A CN 201010150341 CN201010150341 CN 201010150341 CN 201010150341 A CN201010150341 A CN 201010150341A CN 101804989 A CN101804989 A CN 101804989A
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Abstract
The invention relates to a rapid preparation method of a transparent mesoporous silica gel monolith, which belongs to the technical field of the inorganic porous material, in particular to a technical scheme of a simple, efficient, rapid and convenient preparation method of a large-sized, crack-free and optically transparent ordered mesoporous silica gel monolith. The preparation method is characterized in that the direction conversion of gel melting, condensation, aging and drying can be realized at a high temperature through adjusting a synthesis ratio without special protection means and complex operating procedures. Moreover, the method has the advantages of short synthesis period, simple operating steps and easy control. The material prepared in the method has an ordered two-dimensional and hexagonal-phase mesoporous structure, the pore size is 2.0-7.0nm, the pore volume is 0.5-0.8 cm3/g, and the specific surface area is 500-1000m2/g. Therefore, the material has extensive application value in research and development of optical, electrical and magnetic devices.
Description
Technical field
The preparation method of a kind of transparent mesoporous silica gel monolith of the present invention, belong to the inorganic porous material technical field, be specifically related to a kind of quick method for preparing large size, flawless and optical clear mesoporous silica gel monolith that under steady temperature, realizes direct uncovered conversion between colloidal sol-wet gel-xerogel.
Background technology
At present, the synthetic of transparent mesoporous silica gel monolith adopts solvent evaporation method or microemulsion method under the different templates agent is induced to be prepared usually.Produce cracking phenomena for fear of synthesized gel rubber in drying process, slow evaporation, supercritical extraction, vacuum-drying, the introducing inert media of general employing control solvent made the pattern protective material, employing vacuumizes the multistep operation that combines with hydrothermal treatment consists or adopts the methods such as slow gelation process that seal Zha Dong.These methods are generally to the equipment requirements harshness, and energy consumption height, required time are grown (about 8-12 week) very much, or the operation steps complexity is unfavorable for the suitability for industrialized production of this type of material.For example the patent No. is: ZL200310108844.X, the patent No. are: the ZL200410061428.3 and the patent No. are: 2008100550608 invention technical scheme; need to introduce inert media as the pattern protective material; need to adopt complicated vacuumizing and hydro-thermal gelation treating processes; the order that needs to introduce meso-hole structure has the short chain alcohol of destruction to make solubility promoter; need to adopt the slow process that colloidal sol transforms to gel of in having the plastics film sealed vessel of 3-5 pin hole, carrying out; the operational condition harshness; preparation cycle is long, and preparation efficiency is low.
Summary of the invention
The preparation method's of a kind of transparent mesoporous silica gel monolith of the present invention purpose is at above-mentioned deficiency of the prior art, discloses a kind of quick method for preparing large size, flawless and optical clear mesoporous silica gel monolith that realizes direct uncovered conversion between colloidal sol-wet gel-xerogel under steady temperature.
The preparation method of a kind of transparent mesoporous silica gel monolith of the present invention; it is characterized in that it being a kind of by regulating raw material composition proportioning; and under 45-80 ℃ steady temperature scope, prepared colloidal sol and wet gel are carried out encapsulation process; the order that does not need to introduce meso-hole structure has the short chain alcohol of destruction to make solubility promoter; the cumulative volume of reactant is reduced; the required time of system evaporating solvent gelation is shortened; do not need to introduce inert media as the pattern protective material yet; do not need to adopt complicated vacuumizing and hydro-thermal gelation treating processes; do not need to adopt and in having the plastics film sealed vessel of 3-5 pin hole, carry out the large size of colloidal sol to the slow process of gel conversion; the preparation method of flawless and transparent ordered mesoporous silica dioxide gel monolith; concrete processing step is as follows: with nonionogenic tenside P123; Brij56 or F127 and water; acid and silicon source mix; wherein the silicon source is methyl silicate (TMOS); tetraethoxy (TEOS) or positive silicic acid propyl ester (TPOS); the mass ratio of its initial reactant is the silicon source: nonionogenic tenside: water: acid=(1-3): (0.5-2): (0.09-0.27): (0.1-0.3); obtain homogeneous sol after stirring at room 15-30 minute; handled 0.5-1 hour filling under 45-80 ℃, to leave standstill after the container sealing of colloidal sol; directly uncovered then the processing at 45-80 ℃ of following constant temperature made wet gel in 0.5-10 hour; to fill behind the receptacle novel sealing of wet gel still aging 12-24 hour of 45-80 ℃ of following constant temperature; directly uncoveredly then no longer produced weight loss to gel at 45-80 ℃ of following freeze-day with constant temperature 12-48 hour; make optically transparent flawless ordered mesoporous silica dioxide gel monolith; synthesis cycle is 1.5-3 days; institute's synthesizing mesoporous silicon dioxide gel monolith has orderly two dimension six side's phase structures; its aperture is 2.0-7.0nm, and pore volume is 0.5-0.8cm
3/ g, specific surface area is 500-1000m
2/ g, institute's synthesizing mesoporous silicon dioxide gel monolith is suitable to the opticglass of the transmitance of visible light and same thickness, the shape and size that the shape that can be by changing container and the consumption of reactant are regulated the gel monolith that finally obtains, size is greater than 1 * 1 * 0.1cm.
The preparation method of above-mentioned a kind of transparent mesoporous silica gel monolith is characterized in that described acid is hydrochloric acid, sulfuric acid or nitric acid.
The preparation method's of a kind of transparent mesoporous silica gel monolith of the present invention advantage is:
1, passes through the encapsulation process of preparation colloidal sol at 45-80 ℃ of following 0.5-1 hour, can make colloidal sol to the conversion process of gel directly under the uncovered condition at 45-80 ℃ fast (0.5-10 hour) finish, simplified preparation procedure, and the preparation cycle that makes transparent mesoporous silica gel monolith shortens to 1.5-3 days, improved preparation efficiency.
2, (patent No.: ZL200310108844.X) compare, present method need not introduced inert media as the pattern protective material, has simplified operational means with prior art.(patent No.: ZL200410061428.3) compare, present method need not adopt complicated vacuumizing and hydro-thermal gelation treating processes, has simplified synthesis program, has shortened generated time with prior art.And with the prior art (patent No.: 2008100550608) compare, the order that present method need not introduced meso-hole structure has the short chain alcohol of destruction to make solubility promoter, the cumulative volume and the required time of system evaporating solvent gelation of reactant have been reduced simultaneously, particularly pass through synthetic colloidal sol and the constant temperature encapsulation process of wet gel under 45-80 ℃, make system by colloidal sol to gel, by gel to the conversion process of the only stone of xerogel can be under 45-80 ℃ steady temperature direct uncovered carrying out, avoided adopting and in having the plastics film sealed vessel of 3-5 pin hole, carried out the slow process that colloidal sol transforms to gel, simplified operational condition greatly, shorten preparation cycle, improved preparation efficiency.
3, different at the shape of container and reactant consumption, to the time of colloidal sol encapsulation process, the time of system gelation, the time of wet gel seal aging and the final uncovered exsiccant asynchronism(-nization) of gel, are worn out and the exsiccant time is directly proportional at the size of the consumption of reactant and preparation gelinite and required colloidal sol encapsulation process, system gelation.
4, this method synthesis cycle is short, operation steps is simple, and be easy to control, reduced the synthetic difficulty of large size, flawless, optically transparent ordered mesoporous silica dioxide gel monolith, the mesoporous silica gel monolith regular shape that contains tensio-active agent that makes, controllable size, the thermostability and the transparency are good, are suitable for making optical material; Removing the mesoporous silica gel monolith that obtains behind the tensio-active agent is having a wide range of applications aspect catalysis, the separation.
Embodiment
Embodiment 1:
With 1 gram P123,0.18 gram water, 0.2 gram 1M hydrochloric acid and 2.08 gram TEOS form homogeneous sol after mixed at room temperature stirs 30 minutes.Prepared colloidal sol moved in the container with definite shape the sealing back and left standstill 1 hour, container is open to leave standstill under 45 ℃ then and made the system gelation in 5.75 hours in 45 ℃ of following constant temperature.And then, directly 45 ℃ of lower open mouth dryings, obtain complete transparent mesoporous silica gel monolith after 48 hours at last with leaving standstill aging 1 day in 45 ℃ of constant temperature after the container sealing.Be warming up to 550 ℃ and roasting 6 hours to remove the surfactant templates agent fully with the speed of 2 ℃/min again, obtain the only stone material of orderly mesoporous silicon oxide, through XRD, N
2Isothermal adsorption etc. are analyzed test shows, and the gained material has high-quality six side's phase structures, and its specific surface area is 589.71m
2/ g, pore volume are 0.59cm
3/ g, the aperture is 4.6nm.
Embodiment 2:
With 1 gram P123,0.18 gram water, 0.2 gram 1M hydrochloric acid and 2.08 gram TEOS form homogeneous sol after mixed at room temperature stirs 30 minutes.Prepared colloidal sol moved in the container with definite shape the sealing back and left standstill 1 hour, container is open to leave standstill under 60 ℃ then and made the system gelation in 3.5 hours in 60 ℃ of following constant temperature.And then, directly 60 ℃ of lower open mouth dryings, obtain complete transparent mesoporous silica gel monolith after 30 hours at last with leaving standstill aging 1 day in 60 ℃ of constant temperature after the container sealing.Be warming up to 550 ℃ and roasting 6 hours to remove the surfactant templates agent fully with the speed of 2 ℃/min again, other is with embodiment 1.
Embodiment 3:
With 1 gram P123,0.18 gram water, 0.2 gram 1M hydrochloric acid and 2.08 gram TEOS form homogeneous sol after mixed at room temperature stirs 30 minutes.Prepared colloidal sol moved in the container with definite shape the sealing back and left standstill 1 hour, container is open to leave standstill under 80 ℃ then and made the system gelation in 1.5 hours in 80 ℃ of following constant temperature.And then, directly 80 ℃ of lower open mouth dryings, obtain complete transparent mesoporous silica gel monolith after 18 hours at last with leaving standstill aging 1 day in 80 ℃ of constant temperature after the container sealing.Be warming up to 550 ℃ and roasting 6 hours to remove the surfactant templates agent fully with the speed of 2 ℃/min again, obtain the only stone material of orderly mesoporous silicon oxide, through XRD, N
2Isothermal adsorption etc. are analyzed test shows, and the gained material has high-quality six side's phase structures, and its specific surface area is 614.75m
2/ g, pore volume are 0.52cm
3/ g, the aperture is 3.9nm.
Embodiment 4:
With 1 gram Brij56,0.18 gram water, 0.2 gram 1M hydrochloric acid and 2.08 gram TEOS form homogeneous sol after mixed at room temperature stirs 30 minutes.Prepared colloidal sol moved in the container with definite shape the sealing back and left standstill 1 hour, container is open to leave standstill under 45 ℃ then and made the system gelation in 10 hours in 45 ℃ of following constant temperature.And then, directly 45 ℃ of lower open mouth dryings, obtain complete transparent mesoporous silica gel monolith after 48 hours at last with leaving standstill aging 1 day in 45 ℃ of constant temperature after the container sealing.Be warming up to 550 ℃ and roasting 6 hours to remove the surfactant templates agent fully with the speed of 2 ℃/min again, obtain the only stone material of orderly mesoporous silicon oxide, through XRD, N
2Isothermal adsorption etc. are analyzed test shows, and the gained material has high-quality six side's phase structures, and its specific surface area is 1007.4m
2/ g, pore volume are 0.523cm
3/ g, the aperture is 2.2nm.
Embodiment 5:
With 1 gram F127,0.18 gram water, 0.2 gram 1M hydrochloric acid and 2.08 gram TEOS form homogeneous sol after mixed at room temperature stirs 30 minutes.Prepared colloidal sol moved in the container with definite shape the sealing back and left standstill 1 hour, container is open to leave standstill under 45 ℃ then and made the system gelation in 4.5 hours in 45 ℃ of following constant temperature.And then, directly 45 ℃ of lower open mouth dryings, obtain complete transparent meso-porousearth silicon gel monolithi material after 48 hours at last with leaving standstill aging 1 day in 45 ℃ of constant temperature after the container sealing.Be warming up to 550 ℃ and roasting 6 hours to remove the surfactant templates agent fully with the speed of 2 ℃/min again, obtain the only stone material of orderly mesoporous silicon oxide.Through XRD, N
2Isothermal adsorption etc. are analyzed test shows, and the gained material has high-quality six side's phase structures, and its specific surface area is 520.96m
2/ g, pore volume are 0.52cm
3/ g, the aperture is 6.0nm.
Claims (2)
1. the preparation method of a transparent mesoporous silica gel monolith; it is characterized in that it being a kind of by regulating raw material composition proportioning; and under 45-80 ℃ steady temperature scope, prepared colloidal sol and wet gel are carried out encapsulation process; the order that does not need to introduce meso-hole structure has the short chain alcohol of destruction to make solubility promoter; the cumulative volume of reactant is reduced; the required time of system evaporating solvent gelation is shortened; do not need to introduce inert media as the pattern protective material yet; do not need to adopt complicated vacuumizing and hydro-thermal gelation treating processes; do not need to adopt and in having the plastics film sealed vessel of 3-5 pin hole, carry out the large size of colloidal sol to the slow process of gel conversion; the preparation method of flawless and transparent ordered mesoporous silica dioxide gel monolith; concrete processing step is as follows: with nonionogenic tenside P123; Brij56 or F127 and water; acid and silicon source mix; wherein the silicon source is methyl silicate (TMOS); tetraethoxy (TEOS) or positive silicic acid propyl ester (TPOS); the mass ratio of its initial reactant is the silicon source: nonionogenic tenside: water: acid=(1-3): (0.5-2): (0.09-0.27): (0.1-0.3); obtain homogeneous sol after stirring at room 15-30 minute; handled 0.5-1 hour filling under 45-80 ℃, to leave standstill after the container sealing of colloidal sol; directly uncovered then the processing at 45-80 ℃ of following constant temperature made wet gel in 0.5-10 hour; to fill behind the receptacle novel sealing of wet gel still aging 12-24 hour of 45-80 ℃ of following constant temperature; directly uncoveredly then no longer produced weight loss to gel at 45-80 ℃ of following freeze-day with constant temperature 12-48 hour; make optically transparent flawless ordered mesoporous silica dioxide gel monolith; synthesis cycle is 1.5-3 days; institute's synthesizing mesoporous silicon dioxide gel monolith has orderly two dimension six side's phase structures; its aperture is 2.0-7.0nm, and pore volume is 0.5-0.8cm
3/ g, specific surface area is 500-1000m
2/ g, institute's synthesizing mesoporous silicon dioxide gel monolith is suitable to the opticglass of the transmitance of visible light and same thickness, the shape and size that the shape that can be by changing container and the consumption of reactant are regulated the gel monolith that finally obtains, size is greater than 1 * 1 * 0.1cm.
2. the preparation method of above-mentioned a kind of transparent mesoporous silica gel monolith is characterized in that described acid is hydrochloric acid, sulfuric acid or nitric acid.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102976784A (en) * | 2012-12-11 | 2013-03-20 | 太原理工大学 | Green preparation method of transparent mesoporous sial gel monolith |
| CN102992345A (en) * | 2012-12-03 | 2013-03-27 | 太原理工大学 | Preparation method of transparent mesoporous silica-alumina gel monolith |
| CN103159221A (en) * | 2013-03-07 | 2013-06-19 | 太原理工大学 | Preparation method of double-groups modified transparent meso pore silica gel monolith |
| CN103193246A (en) * | 2013-03-07 | 2013-07-10 | 太原理工大学 | Preparation method of transparent mesoporous gel monolith with dual-functional-modified hole walls |
| CN109336118A (en) * | 2018-12-14 | 2019-02-15 | 青岛大学 | A kind of preparation method and products thereof of three-dimensional netted meso-porous titanium dioxide silicon bulk |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101289191A (en) * | 2008-06-05 | 2008-10-22 | 太原理工大学 | Transparent meso-porousearth silicon gel monolithi material |
| WO2009032568A1 (en) * | 2007-09-07 | 2009-03-12 | The Curators Of The University Of Missouri | Pre-formed assemblies of solgel-derived nanoparticles as 3-d scaffolds for composites and aerogels |
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2010
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2009032568A1 (en) * | 2007-09-07 | 2009-03-12 | The Curators Of The University Of Missouri | Pre-formed assemblies of solgel-derived nanoparticles as 3-d scaffolds for composites and aerogels |
| CN101289191A (en) * | 2008-06-05 | 2008-10-22 | 太原理工大学 | Transparent meso-porousearth silicon gel monolithi material |
Non-Patent Citations (1)
| Title |
|---|
| 《J Sol-Gel Sci Techn》 20060627 Jia-Heng Lei et al. Fabrication and characterization of hexagonal mesoporous silica monolith via post-synthesized hydrothermal process 第169-174页 1-2 第39卷, 2 * |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102992345A (en) * | 2012-12-03 | 2013-03-27 | 太原理工大学 | Preparation method of transparent mesoporous silica-alumina gel monolith |
| CN102976784A (en) * | 2012-12-11 | 2013-03-20 | 太原理工大学 | Green preparation method of transparent mesoporous sial gel monolith |
| CN103159221A (en) * | 2013-03-07 | 2013-06-19 | 太原理工大学 | Preparation method of double-groups modified transparent meso pore silica gel monolith |
| CN103193246A (en) * | 2013-03-07 | 2013-07-10 | 太原理工大学 | Preparation method of transparent mesoporous gel monolith with dual-functional-modified hole walls |
| CN103159221B (en) * | 2013-03-07 | 2014-12-10 | 太原理工大学 | Preparation method of double-groups modified transparent meso pore silica gel monolith |
| CN103193246B (en) * | 2013-03-07 | 2015-04-29 | 太原理工大学 | Preparation method of transparent mesoporous gel monolith with dual-functional-modified hole walls |
| CN109336118A (en) * | 2018-12-14 | 2019-02-15 | 青岛大学 | A kind of preparation method and products thereof of three-dimensional netted meso-porous titanium dioxide silicon bulk |
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