CN101804989B - Preparation method of transparent mesoporous silica gel monolith - Google Patents
Preparation method of transparent mesoporous silica gel monolith Download PDFInfo
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- CN101804989B CN101804989B CN2010101503419A CN201010150341A CN101804989B CN 101804989 B CN101804989 B CN 101804989B CN 2010101503419 A CN2010101503419 A CN 2010101503419A CN 201010150341 A CN201010150341 A CN 201010150341A CN 101804989 B CN101804989 B CN 101804989B
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- mesoporous silica
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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, transparent mesoporous silica gel monolith synthetic is employed in solvent evaporation method or the microemulsion method of different templates agent under inducing usually and prepares.In drying process, produce cracking phenomena for fear of synthesized gel rubber, 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 harsh to equipment requirements, and energy consumption is high, required time very long (about 8-12 week), or the operation steps complicacy 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 be employed in to carry out the slow process that colloidal sol transforms to gel in the plastics film sealed vessel that has 3-5 pin hole, and operational condition is harsh; Preparation cycle is long, and preparation efficiency is low.
Summary of the invention
The preparing method's of a kind of transparent mesoporous silica gel monolith of the present invention purpose is to disclose 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 to above-mentioned deficiency of the prior art.
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 through 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 need not introduce meso-hole structure has the short chain alcohol of destruction to make solubility promoter; The TV of reactant is reduced; The required time of system evaporating solvent gelation is shortened, also need not introduce inert media, need not adopt complicated vacuumizing and hydro-thermal gelation treating processes as the pattern protective material; Need not be employed in and carry out the preparation method of colloidal sol in the plastics film sealed vessel that has 3-5 pin hole to large size, flawless and the transparent ordered mesoporous silica dioxide gel monolith of the slow process of gel conversion; Concrete process step is following: nonionogenic tenside P123, Brij56 or F127 and water, acid and silicon source are mixed, and wherein the silicon source is methyl silicate (TMOS), tetraethoxy (TEOS) or positive silicic acid propyl ester (TPOS), and 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 under 45-80 ℃, leaving standstill after the container sealing that fills colloidal sol, directly uncovered then the processing at 45-80 ℃ of following constant temperature made wet gel in 0.5-10 hour, with still wearing out 12-24 hour at 45-80 ℃ of following constant temperature behind the receptacle novel sealing that fills wet gel; 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, and 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 of the gel monolith that the shape that can be through changing container and the consumption adjusting of reactant finally obtain, 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 preparing 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) accomplish; 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 TV and the required time of system evaporating solvent gelation of reactant have been reduced simultaneously; Particularly through to 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 being employed in and carried out the slow process that colloidal sol transforms to gel in the plastics film sealed vessel that has 3-5 pin hole; Simplify operational condition greatly, shortened preparation cycle, improved preparation efficiency.
3, different to 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, the size of the consumption of reactant and preparation gelinite and required colloidal sol encapsulation process, system gelation, wear out and the exsiccant time is directly proportional.
4, this method synthesis cycle is short; Operation steps is simple, and is easy to control, has 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, thermostability is good with the transparency, is 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, then container is open to leave standstill under 45 ℃ 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, then container is open to leave standstill under 60 ℃ 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, then container is open to leave standstill under 80 ℃ 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, then container is open to leave standstill under 45 ℃ 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, then container is open to leave standstill under 45 ℃ 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 through 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 need not introduce meso-hole structure has the short chain alcohol of destruction to make solubility promoter, and the TV of reactant is reduced, and the required time of system evaporating solvent gelation is shortened; Need not introduce inert media as the pattern protective material yet; Need not adopt complicated vacuumizing and hydro-thermal gelation treating processes, need not be employed in and carry out the preparation method of colloidal sol to large size, flawless and the transparent ordered mesoporous silica dioxide gel monolith of the slow process of gel conversion in the plastics film sealed vessel that has 3-5 pin hole, concrete process step is following: nonionogenic tenside P123, Brij56 or F127 and water, acid and silicon source are mixed; 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 with under 45-80 ℃, leaving standstill after the container sealing that fills colloidal sol; Directly uncovered then the processing at 45-80 ℃ of following constant temperature made wet gel in 0.5-10 hour; With behind the receptacle novel sealing that fills wet gel still aging 12-24 hour at 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, and 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 of the gel monolith that the shape through changing container and the consumption adjusting of reactant finally obtain, size is greater than 1 * 1 * 0.1cm.
2. a kind of preparation method of transparent mesoporous silica gel monolith according to claim 1 is characterized in that described acid is hydrochloric acid, sulfuric acid or nitric acid.
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| CN102992345B (en) * | 2012-12-03 | 2014-06-04 | 太原理工大学 | Preparation method of transparent mesoporous silica-alumina gel monolith |
| CN102976784B (en) * | 2012-12-11 | 2014-08-20 | 太原理工大学 | Green preparation method of transparent mesoporous sial 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 |
| 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 |
| CN109336118B (en) * | 2018-12-14 | 2021-05-18 | 青岛大学 | Preparation method of three-dimensional reticular mesoporous silica block and product thereof |
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| CN101289191B (en) * | 2008-06-05 | 2011-04-13 | 太原理工大学 | Transparent meso-porousearth silicon gel monolithi material |
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