CN101890326A - Method for preparing TiO2/SiO2 composite microspheres - Google Patents

Method for preparing TiO2/SiO2 composite microspheres Download PDF

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CN101890326A
CN101890326A CN 201010232212 CN201010232212A CN101890326A CN 101890326 A CN101890326 A CN 101890326A CN 201010232212 CN201010232212 CN 201010232212 CN 201010232212 A CN201010232212 A CN 201010232212A CN 101890326 A CN101890326 A CN 101890326A
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ammoniacal liquor
sio
tio
citric acid
complex microsphere
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CN101890326B (en
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伍媛婷
王秀峰
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Shaanxi University of Science and Technology
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Shaanxi University of Science and Technology
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Abstract

The invention discloses a method for preparing TiO2/SiO2 composite microspheres. In the method, tetraethoxysilane and tetrabutyl titanate are used as raw materials, ammonia water and absolute ethyl alcohol are used as solvents, citric acid is used as a complexing agent and polyethylene glycol is used as a dispersing agent. The method comprises the following steps of: adding Si-containing sol into Ti-containing wet gel with constantly stirring; evaporating in a water bath, drying and foaming to compound the Si-containing sol and the Ti-containing wet gel constantly; and calcining to obtain the TiO2/SiO2 composite microspheres. The method of the invention has short preparation period; and the prepared TiO2/SiO2 composite microspheres are complete spheres of which the particle size is 100 to 900nm and have high purity and yield.

Description

A kind of TiO 2/ SiO 2The preparation method of complex microsphere
Technical field
The invention belongs to technical field of nano material, relate to a kind of TiO 2/ SiO 2The preparation method of complex microsphere.
Background technology
Characteristics such as that titanium dioxide has is nontoxic, harmless, chemical stability is high, opaque, whiteness and glossiness excellence and photocatalytic activity are good, be a kind of good white inorganic pigment and photochemical catalyst, but because the titanium dioxide energy gap is big, need under black light, just can excite the generation electron hole pair, less to the sunshine utilization rate, and exist easily assemble, easily inactivation, be difficult to shortcoming such as recycling.In addition,, when using, easily cause phenomenons such as paint film xanthochromia, efflorescence as coating because there is too strong photocatalytic in titanium dioxide, and TiO 2/ SiO 2Composite granule be able to improve these defectives, thereby widens the application of titanium dioxide.
Present TiO 2/ SiO 2The preparation method of composite comprises sol-gel process, coprecipitation, chemical vapour deposition (CVD) etc.Though chemical vapour deposition technique has short, advantage, its TiO such as cost is lower of cycle 2/ SiO 2Composite material granular exist the particle diameter wider distribution, inhomogeneous, Si/Ti is difficult to mix than wayward and component and cause shortcomings such as the product chemical composition is inhomogeneous.The shortcoming of traditional sol-gel process is that cost is higher, treatment temperature is higher, the easy reunion of predecessor grows up.Coprecipitation production efficiency is lower, the not easily separated control of product, and impurity is more.
Summary of the invention
The technical problem that the present invention solves is to provide a kind of TiO 2/ SiO 2The preparation method of complex microsphere, this method production technology is simple, the cycle is short, equipment is simple, prepared TiO 2/ SiO 2Complex microsphere is a spherical particle, regular shape, better dispersed.
The present invention is achieved through the following technical solutions:
A kind of TiO 2/ SiO 2The preparation method of complex microsphere may further comprise the steps:
1) citric acid is dissolved in the ammoniacal liquor, the amount of ammoniacal liquor is as the criterion can dissolve citric acid, and then according to ethyl orthosilicate: the mol ratio of citric acid=1: 1.5～2 adds ethyl orthosilicate, stirs and makes its dissolving; After waiting to dissolve, add the absolute ethyl alcohol of ammoniacal liquor volume 1/3～1/2 and the polyethylene glycol of citric acid quality 1/3～1/2 more successively, be heated to 50～60 ℃ of stirrings it is dissolved fully; Transfer pH value to 7.0～8.0 with ammoniacal liquor, obtain Sol A;
2) citric acid is dissolved in the ammoniacal liquor, the amount of ammoniacal liquor is as the criterion can dissolve citric acid, and then according to butyl titanate: the mol ratio of citric acid=1: 1.5～2 adds butyl titanate, stirs and makes its dissolving; After waiting to dissolve, add the absolute ethyl alcohol of ammoniacal liquor volume 1/3～1/2 and the polyethylene glycol of citric acid quality 1/3～1/2 more successively, be heated to 50～60 ℃ of stirrings it is dissolved fully; Behind ammoniacal liquor accent pH value to 7.0～8.0,80～90 ℃ of water-baths evaporations are until obtaining wet gel B;
3) be Si: Ti=1 according to mol ratio: 5～7 ratio, Sol A is added among the wet gel B under constantly stirring, in 80～90 ℃ of water-baths, constantly to stir then, evaporation is until obtaining wet gel C;
4) wet gel C is obtained xerogel behind 130～140 ℃ of dry foaming 3～5h, again xerogel is carried out calcining at constant temperature at 600～700 ℃, take out behind calcining 3～5h, obtain TiO 2/ SiO 2Complex microsphere.
Described ammoniacal liquor is that volumetric concentration is 25～28% ammoniacal liquor.
The molecular weight of described polyethylene glycol is 4000 or 6000.
Described wet gel carries out the drying foaming under air atmosphere.
Described xerogel carries out calcining at constant temperature under air atmosphere.
Described TiO 2/ SiO 2Complex microsphere is complete spherical, and granular size is 100～900nm.
Compared with prior art, the present invention has following beneficial technical effects:
The present invention is a raw material with butyl titanate and ethyl orthosilicate, with ammoniacal liquor is solvent, with the citric acid is complexing agent, polyethylene glycol is dispersant (adding absolute ethyl alcohol simultaneously), makes the Sol A that comprises Si respectively and is comprising the wet gel B of Ti, joins among the gel B under Sol A is constantly stirred, in the process of water-bath evaporation preparation wet gel, dry foaming, complex reaction constantly taking place and form network structure, and make titaniferous gel and siliceous gel form clad structure, makes TiO after the calcining at last 2/ SiO 2Complex microsphere.The TiO of gained 2/ SiO 2Complex microsphere is the full spherical of 100～900nm for size, TiO 2Be the core of spherical particle, SiO 2Be compounded in and form TiO on every side 2/ SiO 2Complex microsphere.And, prepared TiO 2/ SiO 2Complex microsphere does not influence TiO 2Photocatalysis, and because circumgranular SiO 2Compound, make composite particles that poly-group be difficult for take place.
In addition, TiO of the present invention 2/ SiO 2There is not impurity such as introducing chlorion in complex microsphere in this preparation process, need not the suction filtration cleaning to remove impurity, can shorten manufacturing cycle; Employed complex compound citric acid, polyethylene glycol and raw material are introduced in preparation is organic substance, can remove fully when calcining, and ethyl orthosilicate, butyl titanate is with whole converted products prepared TiO 2/ SiO 2The purity height of complex microsphere, better dispersed, even particle size, complete shape and appearance, yield rate height.
Description of drawings
Fig. 1 is the TiO of the present invention's preparation 2/ SiO 2The SEM photo of complex microsphere, TiO as can be seen 2/ SiO 2The even particle size of complex microsphere, the sphere of complete shape and appearance.
The specific embodiment
Below in conjunction with accompanying drawing and specific embodiment the present invention is done to describe in further detail, the explanation of the invention is not limited.
Embodiment 1
A kind of TiO 2/ SiO 2The preparation method of complex microsphere may further comprise the steps:
1) citric acid 192.14g (1mol) being dissolved in volumetric concentration is in 25% the 300ml ammoniacal liquor, adds the ethyl orthosilicate of 0.5mol then, stirs to make the ethyl orthosilicate dissolving; After waiting to dissolve, add the absolute ethyl alcohol of 100ml and the polyethylene glycol of 64.05g (PEG4000) more successively, be heated to 50 ℃ of stirrings it is dissolved fully; Transfer pH value to 7.0 with ammoniacal liquor, obtain Sol A;
2) citric acid 192.14g (1mol) being dissolved in volumetric concentration is in 25% the 300ml ammoniacal liquor, adds the butyl titanate of 0.5mol then, stirs to make the butyl titanate dissolving; After waiting to dissolve, add the absolute ethyl alcohol of 100ml and the polyethylene glycol of 64.05g (PEG4000) more successively, be heated to 50 ℃ of stirrings it is dissolved fully; Transfer pH value to 7.0 with ammoniacal liquor, evaporate until obtaining wet gel B 80 ℃ of water-baths;
3) be Si: Ti=1 according to mol ratio: 5 ratio, Sol A is added among the wet gel B under constantly stirring, in 80 ℃ of water-baths, constantly stir then, under situation about mixing, evaporation is until obtaining wet gel C;
4) wet gel C is obtained xerogel behind 130 ℃ of dry foaming 3h, again xerogel is carried out calcining at constant temperature at 600 ℃, take out behind the calcining 5h, obtain TiO 2/ SiO 2Complex microsphere.
Resulting TiO 2/ SiO 2The SEM photo of complex microsphere as shown in Figure 1, TiO as can be seen 2/ SiO 2Complex microsphere is complete spherical, and granular size is 100～900nm.
Embodiment 2
A kind of TiO 2/ SiO 2The preparation method of complex microsphere may further comprise the steps:
1) citric acid 192.14g (1mol) being dissolved in volumetric concentration is in 28% the 300ml ammoniacal liquor, adds the ethyl orthosilicate of 0.67mol then, stirs to make the ethyl orthosilicate dissolving; After waiting to dissolve, add the absolute ethyl alcohol of 150ml and the polyethylene glycol of 96.07g (PEG4000) more successively, be heated to 60 ℃ of stirrings it is dissolved fully; Transfer pH value to 8.0 with ammoniacal liquor, obtain Sol A;
2) citric acid 192.14g (1mol) being dissolved in volumetric concentration is in 28% the 300ml ammoniacal liquor, adds the butyl titanate of 0.67mol then, stirs to make the butyl titanate dissolving; After waiting to dissolve, add the absolute ethyl alcohol of 150ml and the polyethylene glycol of 96.07g (PEG4000) more successively, be heated to 60 ℃ of stirrings it is dissolved fully; Transfer pH value to 8.0 with ammoniacal liquor, evaporate until obtaining wet gel B 90 ℃ of water-baths;
3) be Si: Ti=1 according to mol ratio: 7 ratio, Sol A is added among the wet gel B under constantly stirring, in 90 ℃ of water-baths, constantly to stir then, evaporation is until obtaining wet gel C;
4) wet gel C is obtained xerogel behind 140 ℃ of dry foaming 5h, again xerogel is carried out calcining at constant temperature at 700 ℃, take out behind the calcining 3h, obtain TiO 2/ SiO 2Complex microsphere.
Embodiment 3
A kind of TiO 2/ SiO 2The preparation method of complex microsphere may further comprise the steps:
1) citric acid 192.14g (1mol) being dissolved in volumetric concentration is in 28% the 300ml ammoniacal liquor, adds the ethyl orthosilicate of 0.55mol then, stirs to make the ethyl orthosilicate dissolving; After waiting to dissolve, add the absolute ethyl alcohol of 120ml and the polyethylene glycol of 85g more successively, be heated to 56 ℃ of stirrings it is dissolved fully; Transfer pH value to 7.5 with ammoniacal liquor, obtain Sol A;
2) citric acid 192.14g (1mol) being dissolved in volumetric concentration is in 28% the 300ml ammoniacal liquor, adds the butyl titanate of 0.55mol then, stirs to make the butyl titanate dissolving; After waiting to dissolve, add the absolute ethyl alcohol of 100ml and the polyethylene glycol of 75g more successively, be heated to 50 ℃ of stirrings it is dissolved fully; Transfer pH value to 7.0 with ammoniacal liquor, evaporate until obtaining wet gel B 90 ℃ of water-baths;
3) be Si: Ti=1 according to mol ratio: 6 ratio, Sol A is added among the wet gel B under constantly stirring, in 82 ℃ of water-baths, constantly to stir then, evaporation is until obtaining wet gel C;
4) wet gel C is obtained xerogel behind 135 ℃ of dry foaming 4h, again xerogel is carried out calcining at constant temperature at 620 ℃, take out behind the calcining 3.3h, obtain TiO 2/ SiO 2Complex microsphere.
Embodiment 4
A kind of TiO 2/ SiO 2The preparation method of complex microsphere may further comprise the steps:
1) citric acid 192.14g (1mol) being dissolved in volumetric concentration is in 28% the 300ml ammoniacal liquor, adds the ethyl orthosilicate of 0.65mol then, stirs to make the ethyl orthosilicate dissolving; After waiting to dissolve, add the absolute ethyl alcohol of 135ml and the polyethylene glycol of 70g (PEG6000) more successively, be heated to 52.5 ℃ of stirrings it is dissolved fully; Transfer pH value to 7.46 with ammoniacal liquor, obtain Sol A;
2) citric acid 192.14g (1mol) being dissolved in volumetric concentration is in 28% the 300ml ammoniacal liquor, adds the butyl titanate of 0.60mol then, stirs to make the butyl titanate dissolving; After waiting to dissolve, add the absolute ethyl alcohol of 125ml and the polyethylene glycol of 75g (PEG6000) more successively, be heated to 52.5 ℃ of stirrings it is dissolved fully; Transfer pH value to 7.2 with ammoniacal liquor, evaporate until obtaining wet gel B 85 ℃ of water-baths;
3) be Si: Ti=1 according to mol ratio: 6.5 ratio, Sol A is added among the wet gel B under constantly stirring, in 88 ℃ of water-baths, constantly to stir then, evaporation is until obtaining wet gel C;
4) wet gel C is obtained xerogel behind 136 ℃ of dry foaming 3.5h, again xerogel is carried out calcining at constant temperature at 680 ℃, take out behind the calcining 3.8h, obtain TiO 2/ SiO 2Complex microsphere.
Embodiment 5
A kind of TiO 2/ SiO 2The preparation method of complex microsphere may further comprise the steps:
1) citric acid 192.14g (1mol) being dissolved in volumetric concentration is in 25% the 300ml ammoniacal liquor, adds the ethyl orthosilicate of 0.58mol then, stirs to make the ethyl orthosilicate dissolving; After waiting to dissolve, add the absolute ethyl alcohol of 125ml and the polyethylene glycol of 75g more successively, be heated to 54.5 ℃ of stirrings it is dissolved fully; Transfer pH value to 7.8 with ammoniacal liquor, obtain Sol A;
2) citric acid 192.14g (1mol) being dissolved in volumetric concentration is in 25% the 300ml ammoniacal liquor, adds the butyl titanate of 0.62mol then, stirs to make the butyl titanate dissolving; After waiting to dissolve, add the absolute ethyl alcohol of 150ml and the polyethylene glycol of 80g more successively, be heated to 56 ℃ of stirrings it is dissolved fully; Transfer pH value to 7.2 with ammoniacal liquor, evaporate until obtaining wet gel B 86.5 ℃ of water-baths;
3) be Si: Ti=1 according to mol ratio: 5.5 ratio, Sol A is added among the wet gel B under constantly stirring, in 85 ℃ of water-baths, constantly to stir then, evaporation is until obtaining wet gel C;
4) wet gel C is obtained xerogel behind 132 ℃ of dry foaming 3.8h, again xerogel is carried out calcining at constant temperature at 685 ℃, take out behind the calcining 4.2h, obtain TiO 2/ SiO 2Complex microsphere.

Claims (6)

1. TiO 2/ SiO 2The preparation method of complex microsphere is characterized in that, may further comprise the steps:
1) citric acid is dissolved in the ammoniacal liquor, the amount of ammoniacal liquor is as the criterion can dissolve citric acid, and then according to ethyl orthosilicate: the mol ratio of citric acid=1: 1.5～2 adds ethyl orthosilicate, stirs and makes its dissolving; After waiting to dissolve, add the absolute ethyl alcohol of ammoniacal liquor volume 1/3～1/2 and the polyethylene glycol of citric acid quality 1/3～1/2 more successively, be heated to 50～60 ℃ of stirrings it is dissolved fully; Transfer pH value to 7.0～8.0 with ammoniacal liquor, obtain Sol A;
2) citric acid is dissolved in the ammoniacal liquor, the amount of ammoniacal liquor is as the criterion can dissolve citric acid, and then according to butyl titanate: the mol ratio of citric acid=1: 1.5～2 adds butyl titanate, stirs and makes its dissolving; After waiting to dissolve, add the absolute ethyl alcohol of ammoniacal liquor volume 1/3～1/2 and the polyethylene glycol of citric acid quality 1/3～1/2 more successively, be heated to 50～60 ℃ of stirrings it is dissolved fully; Behind ammoniacal liquor accent pH value to 7.0～8.0,80～90 ℃ of water-baths evaporations are until obtaining wet gel B;
3) be Si: Ti=1 according to mol ratio: 5～7 ratio, Sol A is added among the wet gel B under constantly stirring, in 80～90 ℃ of water-baths, constantly to stir then, evaporation is until obtaining wet gel C;
4) wet gel C is obtained xerogel behind 130～140 ℃ of dry foaming 3～5h, again xerogel is carried out calcining at constant temperature at 600～700 ℃, take out behind calcining 3～5h, obtain TiO 2/ SiO 2Complex microsphere.
2. TiO as claimed in claim 1 2/ SiO 2The preparation method of complex microsphere is characterized in that, described ammoniacal liquor is that volumetric concentration is 25～28% ammoniacal liquor.
3. TiO as claimed in claim 1 2/ SiO 2The preparation method of complex microsphere is characterized in that, the molecular weight of described polyethylene glycol is 4000 or 6000.
4. TiO as claimed in claim 1 2/ SiO 2The preparation method of complex microsphere is characterized in that, described wet gel C carries out the drying foaming under air atmosphere.
5. TiO as claimed in claim 1 2/ SiO 2The preparation method of complex microsphere is characterized in that, described xerogel carries out calcining at constant temperature under air atmosphere.
6. TiO as claimed in claim 1 2/ SiO 2The preparation method of complex microsphere is characterized in that, described TiO 2/ SiO 2Complex microsphere is complete spherical, and granular size is 100～900nm.
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CN104261474A (en) * 2014-09-01 2015-01-07 陕西科技大学 Method for preparing NaLaMgWO6 powder by sol-gel method
CN104772131A (en) * 2014-01-13 2015-07-15 曹雪娟 Freeze-drying type TiO2/SiO2 photocatalytic composite powder and preparation method thereof
CN105314880A (en) * 2015-11-12 2016-02-10 合肥安奎思成套设备有限公司 Preparation method of high-refraction-index glass beads
CN105327683A (en) * 2015-11-11 2016-02-17 欧一鸿 Carbon nanotube printing and dyeing wastewater treatment complexing agent based on SiO<2>/TiO<2> mesoporous composite microsphere carrier and preparation method
CN105366944A (en) * 2015-11-12 2016-03-02 合肥安奎思成套设备有限公司 Preparation method of reflective glass beads
CN105797699A (en) * 2016-05-05 2016-07-27 陕西科技大学 Preparation method of porous silicon dioxide-titanium dioxide bulk material
CN105944706A (en) * 2016-05-05 2016-09-21 陕西科技大学 Preparation method of SiO2-TiO2 porous material
CN105944705A (en) * 2016-05-05 2016-09-21 陕西科技大学 Preparation method of TiO2-SiO2 porous material
CN105964235A (en) * 2016-05-05 2016-09-28 陕西科技大学 Preparation method of porous titanium dioxide-silica block
CN106000426A (en) * 2016-05-31 2016-10-12 河南工业大学 Preparation method of supported sulfuric acid catalyst
CN107163809A (en) * 2017-05-22 2017-09-15 南通卓越纺织涂层有限公司 A kind of fabric insulating moulding coating and preparation method

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1313878A (en) * 1998-08-20 2001-09-19 罗狄亚化学公司 Use of titanium dioxide as anti-UV agent in a rubber composition
EP1279705A1 (en) * 2000-04-06 2003-01-29 Kabushiki Kaisha Toshiba Oxide composite particle and method for its production, phosphor and method for its production, color filter and method for its manufacture, and color display

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1313878A (en) * 1998-08-20 2001-09-19 罗狄亚化学公司 Use of titanium dioxide as anti-UV agent in a rubber composition
EP1279705A1 (en) * 2000-04-06 2003-01-29 Kabushiki Kaisha Toshiba Oxide composite particle and method for its production, phosphor and method for its production, color filter and method for its manufacture, and color display

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
《J.Phys.Chem.》 19951231 Carl Anderson et al. An Improved Photocatalyst of TiO2/SiO2 Prepared by a Sol-Gel Synthesis 第9882-9885页 1-6 第99卷, 第24期 2 *

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CN104772131A (en) * 2014-01-13 2015-07-15 曹雪娟 Freeze-drying type TiO2/SiO2 photocatalytic composite powder and preparation method thereof
CN104772131B (en) * 2014-01-13 2017-11-17 重庆交通大学 Freeze-drying type TiO2/SiO2Photocatalysis composite granule and its preparation method
CN104261474A (en) * 2014-09-01 2015-01-07 陕西科技大学 Method for preparing NaLaMgWO6 powder by sol-gel method
CN104261474B (en) * 2014-09-01 2016-02-10 陕西科技大学 A kind of sol-gel method prepares NaLaMgWO 6the method of powder
CN105327683A (en) * 2015-11-11 2016-02-17 欧一鸿 Carbon nanotube printing and dyeing wastewater treatment complexing agent based on SiO<2>/TiO<2> mesoporous composite microsphere carrier and preparation method
CN105314880A (en) * 2015-11-12 2016-02-10 合肥安奎思成套设备有限公司 Preparation method of high-refraction-index glass beads
CN105366944B (en) * 2015-11-12 2018-10-12 合肥安奎思成套设备有限公司 A kind of preparation method of reflective glass beads
CN105314880B (en) * 2015-11-12 2018-10-12 合肥安奎思成套设备有限公司 A kind of preparation method of high refractive index glass micro pearl
CN105366944A (en) * 2015-11-12 2016-03-02 合肥安奎思成套设备有限公司 Preparation method of reflective glass beads
CN105944705B (en) * 2016-05-05 2018-09-18 陕西科技大学 A kind of TiO2-SiO2The preparation method of porous material
CN105964235A (en) * 2016-05-05 2016-09-28 陕西科技大学 Preparation method of porous titanium dioxide-silica block
CN105797699B (en) * 2016-05-05 2018-07-31 陕西科技大学 A kind of preparation method of porous silica-titanium dioxide bulk
CN105944705A (en) * 2016-05-05 2016-09-21 陕西科技大学 Preparation method of TiO2-SiO2 porous material
CN105944706B (en) * 2016-05-05 2018-09-18 陕西科技大学 A kind of SiO2-TiO2The preparation method of porous material
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CN105944706A (en) * 2016-05-05 2016-09-21 陕西科技大学 Preparation method of SiO2-TiO2 porous material
CN105797699A (en) * 2016-05-05 2016-07-27 陕西科技大学 Preparation method of porous silicon dioxide-titanium dioxide bulk material
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CN107163809A (en) * 2017-05-22 2017-09-15 南通卓越纺织涂层有限公司 A kind of fabric insulating moulding coating and preparation method

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