CN1944251A - Synthetic method for porous silicon dioxide hollow micro ball - Google Patents
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- CN1944251A CN1944251A CN 200610117755 CN200610117755A CN1944251A CN 1944251 A CN1944251 A CN 1944251A CN 200610117755 CN200610117755 CN 200610117755 CN 200610117755 A CN200610117755 A CN 200610117755A CN 1944251 A CN1944251 A CN 1944251A
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Abstract
The present invention relates to synthesis process of hollow porous silicon dioxide micro ball. By means of combining O/W/O emulsion and sol-gel technology, using TEOS as silicon source and HNO3 as TEOS hydrolyzing catalyst, and through catalytic hydrolysis reaction at relatively high temperature, the present invention synthesizes hollow porous silicon dioxide micro ball with kerosene as oil phase and Span-80 as emulsifier. The present invention has simple process and cheap material, and the obtained hollow porous silicon dioxide micro ball has wide application foreground in catalysis, selective separation, dielectric material and other field.
Description
Technical field
The invention belongs to inorganic porous tiny balloon technical field, relate to a kind of novel synthesis of porous silicon dioxide hollow micro ball.
Background technology
Porous silica has high thermostability, hydrothermal stability and bigger specific surface area, and with other material favorable compatibility is arranged, and therefore is subjected to people's extensive concern.Porous silica has been applied to selective separation, catalysis, dielectric substance, prothetic group material etc. at present.In addition, people also are applied to the immobilization of gas adsorption, inorganic materials carrier, enzyme in exploration.
Up to now, the method for preparing tiny balloon mainly contains three kinds: spray method (CN Patent:1 689 557,2005), emulsion method are in conjunction with sol-gel method (CN Patent:1 223 240A, 1999; US Patent:5 376 347,1994; 5 733 567,1998; 4 479 911,1984), (CN Patent:1 480 401,2004 for the sacrificial core method; 1 506 308,2004; 1 772 363A, 2006; US Patent:7 094 369,2006).
Spray method is meant with carrier gas (being generally nitrogen) colloidal sol is written into high-temperature area with the form of small droplets, and the colloidal sol particulate is at high-temperature area generation gelation reaction, thereby a step obtains product.The advantage of this method is that the reaction times is short, only needs several seconds, but the material of non-refractory is had limitation.
With emulsion method and the sol-gel technique synthetic tiny balloon that combines, single stage method and two-step approach dual mode are arranged.When adopting single stage method, conditions such as the hydrolysis rate of the strict control of palpus presoma and pH value, its key is to select suitable reaction raw materials, for example: the synthetic used silicon source of MCM-41 ball need be butyl silicate rather than tetraethoxy.Two-step approach is that emulsion system and sol system mixing are obtained nucleocapsid structure, silicon oxide or other inorganic materials of preparation micron order, sub-micron grade, and in reaction process, the effect of emulsion rapping plate.Two step synthesis methods can obtain target product easily to a certain extent and needn't too much consider selection to raw material type, therefore have more practicality than single stage method, but this class methods existence condition harshness, ingredient requirement height, weak point such as step is many.
The sacrificial core method is with tensio-active agent, inorganic microspheres or colloid micro ball template, adopt hydrothermal treatment consists, sol-gel method or layer-layer self-assembly method to make reaction system form nucleocapsid structure, with methods such as solvent extraction or thermal treatments template is removed at last and obtain tiny balloon.Wherein, it is worth noting layer-layer self-assembly method, this method is with previously prepared nanoparticle or organism, is assembled into microsphere surface by charge effect layer-layer, forms to have nucleocapsid structure.By selecting the different microballoon of particle diameter to make the internal diameter of template control tiny balloon in advance, change the gauge control shell thickness of coated nanoparticle layers.Can obtain the tiny balloon of different inner diameters and shell thickness in this way, and therefore size distribution has more advantage than homogeneous.At present, people utilize this method, have obtained multiple inorganic microspheres, as: SiO
2, Fe
3O
4, TiO
2, zeolite, clay etc.The shortcoming of this method is that the stability of complex operation, product is not so good, more easily caves at removal template process hollow wall.Therefore, people are still continuing the simple and effective tiny balloon synthetic method of research.
Summary of the invention
The object of the present invention is to provide a kind of method of the synthesizing porous SiO 2 hollow microsphere of no template of simple and easy to control, economical rationality.
The present invention proposes a kind of synthetic method of porous silicon dioxide hollow micro ball, and concrete synthesis step is: with TEOS, C
2H
5OH, H
2O and HNO
3According to TEOS (mol): C
2H
5OH (mol): H
2O (mol): HNO
3(mol): Span-80 (g): kerosene (g)=1: (1-6): (15-40): (0.3-0.7): (5-20): ratio (25-60) adds in the reactor in turn, use magnetic stirrer, room temperature hydrolysis 0.5-1.5h, 75-85 ℃ of following hydrolysis 0.5-1h forms heavy-gravity colloidal sol again; Again with the ratio of every mole of TEOS mixing 25-60g kerosene and 5-20gSpan-80, colloidal sol is added in the mixed solution of kerosene under the electric mixer vigorous stirring and sorbyl alcohol Span-80, suction filtration behind the 75-85 ℃ of emulsification 0.5-1.5h, use washing with acetone, obtain the wet gel particle, 75-85 ℃ of dry 20-30h, final program are warmed up to 45 ℃ of-550 ℃ of roasting 8-12h, obtain porous silicon dioxide hollow micro ball.
Among the present invention, stirring velocity is 200-1500rpm.
Among the present invention, use washing with acetone 2-4 time.
The porous silicon dioxide hollow micro ball that synthetic method of the present invention obtains is in catalysis, separation, dielectric substance Application for Field.
The present invention is that O/W/O multiple emulsion and sol-gel are that the sol-gel technology combines with oil/water/oil, is the silicon source with the tetraethoxy, and nitric acid is the teos hydrolysis catalyzer, catalytic hydrolysis reaction under high-temperature not, no template, kerosene are oil phase, and sorbitol monooleate is an emulsifying agent.
Synthetic product of the present invention characterizes through (accompanying drawing 1-6) such as nitrogen absorption, opticmicroscope, scanning electronic microscope, and the SiO 2 hollow microsphere that obtains is described, spherical shell is the abundant meso-hole structure of hole.
When changing synthesis condition, along with the minimizing of nitric acid add-on, particle morphology presents by irregularly shaped particle, defective ball, hollow ball, the solid sphere variation tendency to the ball of reuniting, and illustrates that the nitric acid add-on has very big influence to the product pattern; Increase C
2H
5The add-on of OH, particle morphology have presented by hollow ball, to irregular particle, arrive the variation tendency of reunion microballoon again; Span-80 plays the effect of true emulsion structure as emulsifying agent in emulsion system.When the emulsifying agent consumption is very few, form the bigger irregular reunion ball of particle diameter.Along with the emulsifying agent consumption increases, the particle of formation is a solid construction.When the emulsifying agent add-on is suitable, then obtain the microballoon of regular shape, smooth surface, and structure is hollow.The add-on of emulsifying agent is increased to 20g, can obtains slick tiny balloon equally, particle diameter is slightly little.As corresponding 1 mole of TEOS, when the Span-80 add-on is respectively 5g, 10g, 15g, 20g, the product particle diameter from about the 500 μ m to tens microns; Along with the increase of kerosene add-on, all obtain tiny balloon, only particle diameter is from large to small; In the low whipping speed scope, all can obtain more perfect tiny balloon, and along with the increase of stirring velocity, the particle diameter of particle reduces gradually, illustrates that stirring velocity only has certain influence to size.Adopt kerosene and Span-80 emulsion system and sol-gel method to combine, under high-speed stirring condition of the present invention, can prepare particle diameter and be several microns microballoon.
Therefore, sol-gel method and O/W/O multiple emulsion system are combined, prepare the method for tiny balloon, also can be applied to the system that gelation reaction can take place for other.
The advantage of the inventive method is: by changing proportioning raw materials, can obtain the mesopore silica dioxide hollow sphere of different-shape and specific surface area.Product can be brought into play important application in the fields such as design of the embedding of catalysis, absorption, separation, medicine and slowly-releasing, artificial cell.The inventive method is compared with traditional method, and is simple and easy to control, do not need to add template, the reaction conditions gentleness, and raw material is cheap and easy to get, and the cost economical rationality has improved preparation efficiency, and quality product and yield rate all are guaranteed.
Description of drawings
Fig. 1 is HNO
3Add-on is to the influence of product pattern, wherein n (HNO
3)/n (TEOS)=0.5.
Fig. 2 is C
2H
5OH is to the influence of product pattern, wherein n (C
2H
5OH)/n (TEOS)=2.
Fig. 3 is the TEM figure of mesoporous silica spheres shell.
Embodiment
Embodiment 1:
At TEOS (mol): C
2H
5OH (mol): H
2O (mol): Span-80 (g): kerosene (g)=1: 3: 20: under 15: 40 conditions, change adding HNO
3Mole number, at n (HNO
3)/n (TEOS) is 0.5 o'clock, and product is a hollow ball, as shown in Figure 1.
Embodiment 2:
At TEOS (mol): H
2O (mol): HNO
3(mol): Span-80 (g): kerosene (g)=1: 20: 0.5: under 15: 40 conditions, the TEOS consumption is 6ml, changes C
2H
5The add-on of OH is at n (C
2H
5OH)/and n (TEOS) is 2 o'clock, and product is a hollow ball, and the SEM photo of product is as shown in Figure 2.
Embodiment 3:
At TEOS (mol): C
2H
5OH (mol): H
2O (mol): HNO
3(mol): kerosene (g)=1: 3: 20: under 0.5: 40 condition, the TEOS consumption is 6ml, changes the add-on of Span-80, and when Span-80 was 20g/mol TEOS, product was a hollow ball.
Embodiment 4:
At TEOS (mol): C
2H
5OH (mol): H
2O (mol): HNO
3(mol): Span-80 (g)=1: 3: 20: under 0.5: 15 condition, the TEOS consumption is 6ml, changes the kerosene add-on, and when kerosene was 60g/mol TEOS, product was a hollow ball.
Embodiment 5:
At TEOS (mol): C
2H
5OH (mol): H
2O (mol): HNO
3(mol): Span-80 (g): kerosene (g)=1: 3: 20: under 0.5: 15: 40 condition, the TEOS consumption is 6ml, changes emulsification stirring speed, is respectively 200,250,300,400, during 500rpm, and product is a hollow ball.
Claims (4)
1, a kind of synthetic method of porous silicon dioxide hollow micro ball is characterized in that oil/water/oily multiple emulsion and sol-gel technique are being combined, and is the silicon source with tetraethoxy TEOS, nitric acid HNO
3Be the TEOS hydrolyst, catalytic hydrolysis reaction, no template is an oil phase at kerosene, and sorbitol monooleate Span-80 is synthetic obtaining under the emulsifying agent, and concrete synthesis step is: with TEOS, C
2H
5OH, H
2O and HNO
3Add in turn in the reactor, stir, room temperature hydrolysis 0.5-1.5h, 75-85 ℃ of following hydrolysis 0.5-1h forms heavy-gravity colloidal sol again; Then colloidal sol is added in the mixed solution of kerosene under the agitator vigorous stirring and sorbyl alcohol Span-80, suction filtration behind the 75-85 ℃ of emulsification 0.5-1.5h, use washing with acetone, obtain the wet gel particle, 75-85 ℃ of dry 20-30h, final program is warmed up to 45 ℃ of-550 ℃ of roasting 8-12h, obtains porous silicon dioxide hollow micro ball, and the mol ratio of above-mentioned reactant is TEOS: C
2H
5OH: H
2O: HNO
3=1: 1-6: 15-40: 0.3-0.7, the used kerosene of every mole of TEOS, the weight of sorbitol monooleate Span-80 are respectively 25-60g, 5-20g.
2, synthetic method as claimed in claim 1 is characterized in that stirring velocity is 200-1500rpm.
3, synthetic method as claimed in claim 1 is characterized in that using washing with acetone 2-4 time.
4, the porous silicon dioxide hollow micro ball of synthetic method acquisition as claimed in claim 1 is in catalysis, separation, dielectric substance Application for Field.
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| CN101792149A (en) * | 2010-03-16 | 2010-08-04 | 南开大学 | Spherical silicon dioxide hollow material and preparation method thereof |
| CN101811014A (en) * | 2010-04-01 | 2010-08-25 | 西安科技大学 | Method for preparing microcapsule |
| CN101475184B (en) * | 2009-01-15 | 2010-11-10 | 北京航空航天大学 | Preparation of inorganic magnetic material for filling hollow mesoporous silicon dioxide sphere |
| CN101632913B (en) * | 2009-07-09 | 2011-07-27 | 上海交通大学 | Preparation method of silicon/porous carbon nano-composite particle |
| CN102553501A (en) * | 2011-12-29 | 2012-07-11 | 中国文化遗产研究院 | Method for preparing supported corrosion inhibitor |
| CN102060300B (en) * | 2009-11-13 | 2013-01-16 | 中国科学院上海硅酸盐研究所 | Method for synthesizing high-dispersibility high-specific surface area large-pore volume SiO2 hollow spheres |
| CN102936015A (en) * | 2012-11-23 | 2013-02-20 | 苏州知益微球科技有限公司 | Preparation method of silica gel microspheres |
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| CN101475184B (en) * | 2009-01-15 | 2010-11-10 | 北京航空航天大学 | Preparation of inorganic magnetic material for filling hollow mesoporous silicon dioxide sphere |
| CN101632913B (en) * | 2009-07-09 | 2011-07-27 | 上海交通大学 | Preparation method of silicon/porous carbon nano-composite particle |
| CN102060300B (en) * | 2009-11-13 | 2013-01-16 | 中国科学院上海硅酸盐研究所 | Method for synthesizing high-dispersibility high-specific surface area large-pore volume SiO2 hollow spheres |
| CN101792149A (en) * | 2010-03-16 | 2010-08-04 | 南开大学 | Spherical silicon dioxide hollow material and preparation method thereof |
| CN101811014A (en) * | 2010-04-01 | 2010-08-25 | 西安科技大学 | Method for preparing microcapsule |
| CN102553501A (en) * | 2011-12-29 | 2012-07-11 | 中国文化遗产研究院 | Method for preparing supported corrosion inhibitor |
| CN102936015A (en) * | 2012-11-23 | 2013-02-20 | 苏州知益微球科技有限公司 | Preparation method of silica gel microspheres |
| CN104785789A (en) * | 2015-04-16 | 2015-07-22 | 柳州豪祥特科技有限公司 | Silicon-mixed tungsten powder preparation process |
| CN105883829A (en) * | 2016-03-31 | 2016-08-24 | 武汉工程大学 | Method for synthesizing onion mesoporous silica nanometer material |
| CN107311185A (en) * | 2017-06-23 | 2017-11-03 | 复旦大学 | A kind of preparation method of superelevation porosity porous silica |
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| CN107486109A (en) * | 2017-09-05 | 2017-12-19 | 广西科技师范学院 | A kind of CdS/g C3N4The preparation method of tiny balloon |
| CN108249451A (en) * | 2018-03-15 | 2018-07-06 | 东莞市真思电子有限公司 | A kind of synthesizing preparation method in situ of virtual acoustic material |
| CN111232991A (en) * | 2020-04-08 | 2020-06-05 | 天津纳科世纪新材料有限公司 | Silica aerogel spherical powder with special structure and preparation method thereof |
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| CN100372763C (en) | 2008-03-05 |
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