CN1092147C - Process for preparing uniform compound monodispersed nm-class spherical TiO2 particles - Google Patents
Process for preparing uniform compound monodispersed nm-class spherical TiO2 particles Download PDFInfo
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- 239000002245 particle Substances 0.000 title claims abstract description 76
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title claims abstract description 70
- 150000001875 compounds Chemical class 0.000 title description 12
- 238000004519 manufacturing process Methods 0.000 title description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 47
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 44
- 239000004408 titanium dioxide Substances 0.000 claims abstract description 29
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 29
- 229910001868 water Inorganic materials 0.000 claims abstract description 29
- 229910021529 ammonia Inorganic materials 0.000 claims abstract description 23
- 238000000034 method Methods 0.000 claims abstract description 23
- 238000002156 mixing Methods 0.000 claims abstract description 20
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 18
- 239000002131 composite material Substances 0.000 claims abstract description 14
- 235000012239 silicon dioxide Nutrition 0.000 claims abstract description 12
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 11
- 238000003756 stirring Methods 0.000 claims abstract description 9
- 235000011114 ammonium hydroxide Nutrition 0.000 claims abstract description 7
- 239000003495 polar organic solvent Substances 0.000 claims abstract description 7
- 239000012798 spherical particle Substances 0.000 claims abstract 7
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims abstract 2
- JEGUKCSWCFPDGT-UHFFFAOYSA-N h2o hydrate Chemical compound O.O JEGUKCSWCFPDGT-UHFFFAOYSA-N 0.000 claims abstract 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical group CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 42
- 239000010936 titanium Substances 0.000 claims description 19
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 18
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 17
- 229960004756 ethanol Drugs 0.000 claims description 17
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 15
- 239000002244 precipitate Substances 0.000 claims description 15
- 238000002360 preparation method Methods 0.000 claims description 15
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 11
- 229960000935 dehydrated alcohol Drugs 0.000 claims description 5
- 239000000843 powder Substances 0.000 claims description 5
- 229910052719 titanium Inorganic materials 0.000 claims description 5
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 claims description 3
- 239000002105 nanoparticle Substances 0.000 claims description 2
- 239000002904 solvent Substances 0.000 abstract description 15
- 238000006243 chemical reaction Methods 0.000 abstract description 11
- 150000002148 esters Chemical class 0.000 abstract description 3
- LLZRNZOLAXHGLL-UHFFFAOYSA-J titanic acid Chemical compound O[Ti](O)(O)O LLZRNZOLAXHGLL-UHFFFAOYSA-J 0.000 abstract 1
- 235000010215 titanium dioxide Nutrition 0.000 description 28
- 229910010413 TiO 2 Inorganic materials 0.000 description 23
- 239000008187 granular material Substances 0.000 description 21
- 238000005119 centrifugation Methods 0.000 description 14
- 238000001556 precipitation Methods 0.000 description 13
- -1 transmitter Substances 0.000 description 12
- 229910004298 SiO 2 Inorganic materials 0.000 description 11
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 11
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 description 10
- 239000010703 silicon Substances 0.000 description 9
- 229910052710 silicon Inorganic materials 0.000 description 9
- 238000001291 vacuum drying Methods 0.000 description 9
- JMXKSZRRTHPKDL-UHFFFAOYSA-N titanium ethoxide Chemical compound [Ti+4].CC[O-].CC[O-].CC[O-].CC[O-] JMXKSZRRTHPKDL-UHFFFAOYSA-N 0.000 description 8
- 229960001866 silicon dioxide Drugs 0.000 description 7
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 7
- 241000237502 Ostreidae Species 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 235000020636 oyster Nutrition 0.000 description 6
- 238000000576 coating method Methods 0.000 description 5
- 230000007062 hydrolysis Effects 0.000 description 5
- 238000006460 hydrolysis reaction Methods 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 239000003973 paint Substances 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 239000006185 dispersion Substances 0.000 description 4
- 239000000049 pigment Substances 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 3
- 150000004703 alkoxides Chemical class 0.000 description 3
- 239000011324 bead Substances 0.000 description 3
- 238000005660 chlorination reaction Methods 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 229910010272 inorganic material Inorganic materials 0.000 description 3
- 239000011147 inorganic material Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000012046 mixed solvent Substances 0.000 description 3
- 238000007639 printing Methods 0.000 description 3
- 239000004065 semiconductor Substances 0.000 description 3
- 238000005245 sintering Methods 0.000 description 3
- 241001502050 Acis Species 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical class CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000011247 coating layer Substances 0.000 description 2
- 239000003989 dielectric material Substances 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 229920001971 elastomer Polymers 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 235000013305 food Nutrition 0.000 description 2
- 235000011194 food seasoning agent Nutrition 0.000 description 2
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- 229920003023 plastic Polymers 0.000 description 2
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 description 2
- 239000005995 Aluminium silicate Substances 0.000 description 1
- 241000790917 Dioxys <bee> Species 0.000 description 1
- 206010034972 Photosensitivity reaction Diseases 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 230000001476 alcoholic effect Effects 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
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- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 235000012204 lemonade/lime carbonate Nutrition 0.000 description 1
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- Inorganic Compounds Of Heavy Metals (AREA)
- Silicon Compounds (AREA)
Abstract
本发明涉及粒径在55～1400nm复合单分散均匀球形二氧化钛颗粒的制备方法，将二氧化硅颗粒用超声或搅拌分散到极性有机溶剂中，其重量与溶剂的体积比为3～100克/升；再在上述溶液中加入水和/或氨水，然后加入钛酸酯，使混合后的氨的初始体积摩尔浓度为0.001～1摩尔/升，水的为0.01～3摩尔/升，钛酸酯的为0.005～0.5摩尔/升，在25～45℃下反应3～48小时，得到复合单分散均匀纳米二氧化钛球型颗粒。本发明得到的颗粒纯度高，分散性好，且产物的尺寸可通过反应条件加以控制。The invention relates to a method for preparing composite monodisperse uniform spherical titanium dioxide particles with a particle diameter of 55-1400 nm. The silicon dioxide particles are dispersed into a polar organic solvent by ultrasonic or stirring, and the volume ratio of the weight to the solvent is 3-100 g/ liter; then add water and/or ammonia water to the above solution, and then add titanate, so that the initial volume molar concentration of ammonia after mixing is 0.001-1 mol/liter, that of water is 0.01-3 mol/liter, and that of titanic acid The concentration of the ester is 0.005-0.5 mol/liter, and the reaction is carried out at 25-45° C. for 3-48 hours to obtain composite monodisperse uniform nanometer titanium dioxide spherical particles. The particles obtained by the invention have high purity and good dispersibility, and the size of the product can be controlled through reaction conditions.
Description
The invention belongs to the preparation and the applied technical field of the inorganic smooth function nano material of semi-conductor, particularly relate to the preparation method of uniform compound monodispersed nm titanium dioxide granule.
TiO
2The popular name titanium dioxide is a kind of more high function fine inorganic material of studying, and is important pottery, semi-conductor and catalytic material, and nano-TiO
2Have more particular performances such as good weathering resistance, chemical resistance, higher chemical stability, thermostability, nontoxicity, photosensitivity, high dispersive and non-migrating and be widely used in fields such as high grade paint, transmitter, dielectric materials, plastics, printing ink, papermaking, chemical fibre and rubber, for example:
(1) nano-TiO
2Have very important optical property---color reaction, and make its extremely the automobile finish expert favor and become the most high-grade effect pigment in the present age.The auto maker that Ford, Chrysler, Toyota, Mazda etc. are famous uses and contains nano-TiO
2Metal car finish paint, this finish paint is coated in the artistic effect that can reach a kind of very graceful fineness on the automobile, and world car industry car over half is all used the application of metal finish paint, to containing nano-TiO
2Metal flash paint require very big.
(2) because nano-TiO
2Characteristics such as existing visible light penetrativity is strong, and is transparent and nontoxic have excellent ultraviolet shielded effect and peculiar colour effect again, available its preparation sunscreen skincare product, and be added in the food product packing film, can make the food matter that remains unchanged for a long period of time, than organic additive obvious superiority is arranged.
(3) nano-TiO
2The specific surface atomicity sharply increases, and the reactive behavior height is so can be used as light-sensitive catalyst, sorbent material.
(4) nano-TiO
2Fusing point is than general T iO
2Low, and uniform particles, can reach tight filling, so can be as good fine ceramics sintering aid.
In addition, nano-TiO
2Can be as the additive of the strengthening agent of the tinting material of the nucleus agent of special glass, resin printing ink, silicon rubber, solid lubricant, matting agent, catalyzer etc.Nano-TiO
2Specific function and purposes and more than these, still among research and development constantly.
Existing in the world at present company more than 10 is at development and production superfine Ti O
2, and Japanese firm is in the majority, its production method mainly is a chlorination process.Chlorination process is with TiCl
4Make superfine Ti O with the oxygen reaction
2But chlorination process needs the raw material of high-grade, and its price just becomes the factor of restriction development.And China is in the early stage of development of titanium dioxide, and production and technology do not break away from the primary stage as yet, do not form scale operation.At present the China's titanium white powder mainly adopts sulfuric acid process, and the kind of product is few, and retaining is time low, and whiteness is bad, mixed crystal, and tinting strength is bad, and granularity is poor, and the production cost height can't satisfy the needs of domestic market and needs to rely on import.The report of this respect is referring to the article " technological transformation of opinion China sulfate process titanium dioxide factory " of 1997 the 6th phases " coatings industry " magazine 19-20 page or leaf.
TiO
2Particle is during as the pigment of excellence and some special purposes, the just particulate outside surface that reality can be utilized and play a role, the kernel of particle then not performance effect should be arranged, the therefore TiO that exists with interior kernel form
2The cost height is actually a kind of huge waste of resource.People actively seek the way that addresses this problem for many years, so the production technology of bag nuclear titanium dioxide pigment occurred.The kernel of existing bag nuclear titanium white is generally used lime carbonate, kaolin, mica etc.Its production method is physics method and chemical method and chemical physics synthetic method.Yet these methods all exist coating not exclusively, and the excessive use meeting of coating is to TiO
2Performance produce negative shortcomings such as influence, and the quality of inner nuclear material and the uneven problem of size-grade distribution that coats titanium white be the key issue of producing bag nuclear titanium white always, and the report of this respect is referring to the article " know-why and developing direction that bag nuclear titanium dioxide pigment is produced " of 1997 the 9th phases " coatings industry " magazine 1-3 page or leaf.
In addition, prepare TiO with the metal alkoxide hydrolysis method
2Energy consumption is low, the product purity height, but particle diameter is difficult to control, and repeatability is difficult to grasp, and is easy to reunite, and is difficult for making the controlled TiO that singly is uniformly dispersed of particle diameter simultaneously
2Particle.This respect content is referring to " Journal of Inorganic Materials " nineteen ninety-five the 10th volume, and " alkoxide hydrolysis prepares TiO to the article of the 4th phase
2Nano-powder ".
The objective of the invention is to overcome the shortcoming of above the whole bag of tricks, a kind of method for preparing purity height, single dispersion, narrow diameter distribution, uniform particles, composite nano titanium dioxide spheroidal particle that the particle diameter controlled range is big is provided.Adopt method of the present invention can prepare singly the be uniformly dispersed nm-class spherical TiO 2 particles of particle diameter at 55～1400nm.
The objective of the invention is to be achieved through the following technical solutions:
Prepare composite Nano TiO with the metal alkoxide hydrolysis method
2Even monodisperse sphere type particle, this particle are at single 50～1300 nanometer spherical SiO of dispersion as kernel
2Coat last layer desired thickness (5～200nm) TiO on the particle
2, make former SiO
2Particle has the character of titanium dioxide granule.
Concrete preparation method is as follows:
With silica dioxide granule with ultrasonic or dispersed with stirring in polar organic solvent, wherein the particle diameter of silica dioxide granule is 50～1300nm, is preferably 50～950nm, the volume ratio of its weight and solvent is 3～100 grams per liters, is preferably 3～50 grams per liters; In above-mentioned solution, add entry and/or ammoniacal liquor again, add titanic acid ester [Ti (OR) then
4], making the original volume volumetric molar concentration of mixed ammonia for a short time is 0.001～1 mol, is preferably 0.001～0.5 mol; The original volume volumetric molar concentration of water is 0.01～3 mol, is preferably 0.015～2 mol; The original volume volumetric molar concentration of titanic acid ester is 0.005～0.5 mol, be preferably 0.005～0.3 mol, reacted 3～48 hours down, obtain oyster white or white opacity solution at 25～45 ℃, centrifugation again, obtain uniform compound monodispersed nm-class spherical TiO 2 particles, particle diameter is band glossy white precipitate at 55～1400nm, the vacuum-drying of gained precipitation, or under 450-800 ℃, roast thermal treatment 0.5～1 hour obtains the titanium dioxide powder of rutile-type or anatase titanium dioxide.
Wherein said titanic acid ester [Ti (OR)
4] in R be-C
nH
2n+1, n=2～4; Described polar organic solvent is in the mixed solvent of any solvent in dehydrated alcohol, acetone, acetonitrile, Virahol, ethylene glycol or ethanol and acetone, acetonitrile, Virahol and the ethylene glycol, and its blended volume ratio is 1: 1～5: 1.
Described silica dioxide granule can commercially availablely obtain or adopt the hydrolysis method preparation of Stober to obtain, this method is rolled up the 62nd～69 page article (Werner Stober referring to " colloidal interface science magazine " nineteen sixty-eight the 26th, Arthur FinkandErnst Bohn Controlled Growth of Monodisperse Silica Spheres in the Micron Size Range, Journal of Colloid and Interface Science 26,6269 (1968)), the single SiO that disperses of the preparation of hydrolysis silicon ester in alcohol-ammonia medium of people such as Stober proposition
2Method, become people and studied the method that generally adopts when monodisperse system forms mechanism, be characterized in, be easy to select within the specific limits synthetic required particle grain size.Among the present invention it has been carried out modification, concrete preparation method is as follows:
With ammonia, water and silicon ester [Si (OR)
4] be added in solvent such as the alcohol, making the original volume volumetric molar concentration of mixing back ammonia is 0.5～9 mol, is preferably 0.5～7 mol; The original volume volumetric molar concentration of water is 1～20 mol, is preferably 1～15 mol; Silicon ester [Si (OR)
4] the original volume volumetric molar concentration be 0.01～1.5 mol, be preferably 0.1～1.0 mol; The molarity of the alcoholic solution of silicon ester determines that according to the size of desired silicon dioxide sub-micron grade particles grain diameter increases with the increase of used silicon ester consumption usually.Above-mentioned mixing solutions is at room temperature stirred down reaction 0.5～24 hour, obtain turbid solution; With this turbid solution centrifugation, obtain white depositions silicon-dioxide then, precipitation of silica with small amount of ethanol washing 1～2 time, is finally obtained SiO
2Particle, its particle diameter be in 50～1300 nanometers, preferred 50～950 nanometers, last SiO
2Particle can leave in ethanol, acetone, butanols, Virahol or the ethylene glycol solvent; Or deposit in the solution of water and ammonia; Or vacuum or seasoning preservation.
Wherein said silicon ester [Si (OR)
4] in R be-C
nH
2n+1, n=1～5 are preferably positive tetraethyl orthosilicate [Si (OC
2H
5)
4], solvent alcohol is ethanol, butanols or Virahol.
Description of drawings:
The composite titanium dioxide bead electromicroscopic photograph of Fig. 1-embodiments of the invention 1
Fig. 2-embodiments of the invention 2 composite titanium dioxide bead electromicroscopic photographs
Fig. 3-embodiments of the invention 3 composite titanium dioxide bead electromicroscopic photographs
Effect of the present invention and advantage:
The SiO that adopts method of the present invention to obtain2Particle uniform particles, the single dispersion are such as accompanying drawing 1, accompanying drawing 2 and attached Shown in Figure 3; But the coverage degree to each particle is measured, and the titanium elements that coats on each particle reaches 4～55 % (weight). The weight of silicon and titanium elements content in the single titanium dioxide granule of gained among embodiment 1 and the embodiment 6 Amount percentage sees Table 1:
Table 1
| Element | % by weight | Deviation | |
| Embodiment 1 | Si | 95.72 | 0.363 |
| Ti | 4.28 | 0.08 | |
| Embodiment 6 | Si | 53.52 | 0.597 |
| Ti | 46.48 | 0.576 |
Hydrolyze method of the present invention not only energy consumption is low, the product purity height, evenly, good dispersion, and the size of particle not only can be by preparing in advance kernel dispersed nano spherical SiO2The reaction condition of particle is controlled, and also can pass through TiO2Coating layer thickness is controlled.
The present invention prepares composite Ti O2Method simple, be easy to apply. By with the concentration of esters of silicon acis and The proportioning of water, ammonia is controlled the size of silica dioxide granule particle diameter. By coming with the concentration of titanate esters and the proportioning of water Control the coating layer thickness of titanium dioxide, be easier to make the titanium dioxide of nanoscale monodisperse spherical. With comparatively inexpensive Esters of silicon acis prepare nanometer silicon dioxide particle, prepare monodispersed titanium dioxide with silica dioxide granule as kernel again The method of titanium is very economical and superior. Solvent for use is inexpensive, be easy to get, and safety is recyclable.
What the method was significantly different from the past preparation method is that in the present invention, the preparation of titania nanoparticles is in the spherical SiO that singly is uniformly dispersed as kernel2Evenly apply last layer TiO on the particle2, make particle have dioxy Change the character of titanium.
Purposes of the present invention: product purpose of the present invention is extensive, be high function fine inorganic material, important pottery, Semiconductor and catalysis material are widely used in coating, sensor, dielectric material, plastics, printing ink, papermaking, change The fields such as fibre, rubber.
The present invention is further described by the following embodiment:
Embodiment 1
With ammonia, water and tetraethyl silicate [Si (OC
2H
5)
4] be added in the etoh solvent, making the original volume volumetric molar concentration of mixing back ammonia is 3 mol, and the original volume volumetric molar concentration of water is 7 mol, and the original volume volumetric molar concentration of tetraethyl silicate is 0.25 mol, above-mentioned mixing solutions is at room temperature stirred down reaction 24 hours, obtain turbid solution; With this turbid solution centrifugation, obtain the silicon-dioxide white precipitate then, precipitation of silica with small amount of ethanol washing 2 times, is finally obtained SiO
2Particle, its particle diameter be in 320 nanometers, last SiO
2Particle can leave in the ethanol; Used solvent is recyclable.
50 gram silica dioxide granules are risen in the dehydrated alcohol with dispersed with stirring to 1; In above-mentioned solution, add entry and 25% ammoniacal liquor again, add tetrabutyl titanate [Ti (OC then
4H
9)
4], the original volume volumetric molar concentration that makes mixed ammonia is 0.01mol/L, and the original volume volumetric molar concentration of water is 0.06mol/L, and the original volume volumetric molar concentration of tetrabutyl titanate is 0.015mol/L, reacted 12 hours down at 35 ℃, obtain white opacity solution, centrifugation again obtains being with the glossy white precipitate, the vacuum-drying of gained precipitation, obtain uniform compound monodispersed nm-class spherical TiO 2 particles, particle diameter promptly clads the titanium dioxide granule of about 8 nanometers of thickness in 328 nanometers.See accompanying drawing 1.
Embodiment 2
The 35 gram silica dioxide granules that obtain among the embodiment 1 are distributed in 1 liter of dehydrated alcohol again with stirring; In above-mentioned solution, add 25% ammoniacal liquor again, add tetrabutyl titanate [Ti (OC then
4H
9)
4], the original volume volumetric molar concentration that makes mixed water is 0.1mol/L, the original volume volumetric molar concentration of tetrabutyl titanate is 0.03mol/L, reacts 12 hours down at 35 ℃, obtains oyster white or white opacity solution, centrifugation again, obtain being with the glossy white precipitate, the vacuum-drying of gained precipitation obtains uniform compound monodispersed nm-class spherical TiO 2 particles, particle diameter promptly clads the titanium dioxide granule of about 30 nanometers of thickness in 352 nanometers.See accompanying drawing 2.
Embodiment 3
With ammonia, water and positive tetraethyl orthosilicate [Si (OC
2H
5)
4] be added in the etoh solvent, making the original volume volumetric molar concentration of mixing back ammonia is 4 mol, the original volume volumetric molar concentration of water is 11 mol, the original volume volumetric molar concentration of positive tetraethyl orthosilicate is 0.5 mol, above-mentioned mixing solutions is at room temperature stirred down reaction 8 hours, obtain turbid solution; With this turbid solution centrifugation, obtain the silicon-dioxide white precipitate then, precipitation of silica with small amount of ethanol washing 1 time, is finally obtained SiO
2Particle, its particle diameter be in 580 nanometers, last SiO
2The particle seasoning is preserved.
30 gram silica dioxide granules are risen in ethanol and the isopropyl alcohol mixed solvent with dispersed with stirring to 1; The volume ratio of ethanol and Virahol is 1: 1, adds entry again in above-mentioned solution, adds isopropyl titanate [Ti (i-OC then
3H
7)
4], the original volume volumetric molar concentration that makes mixed water is 0.4mol/L, isopropyl titanate [Ti (i-OC
3H
7)
4] the original volume volumetric molar concentration be 0.09mol/L, reacted 4 hours down at 45 ℃, obtain oyster white or white opacity solution, centrifugation again, obtain being with the glossy white precipitate, the vacuum-drying of gained precipitation obtains uniform compound monodispersed nm-class spherical TiO 2 particles, particle diameter promptly clads the titanium dioxide granule of about 70 nanometers of thickness in 650 nanometers.See accompanying drawing 3.Sintering carries out half an hour at 750 ℃, obtains the titanium dioxide powder of rutile-type.
Embodiment 4
In the commercially available mixed solvent of 5 gram silica dioxide granules (particle diameter 500 nanometers) with ultra-sonic dispersion to 200 milliliter ethanol and acetone; The volume ratio of ethanol and acetone is 7: 3, adds entry again in above-mentioned solution, adds tetraethyl titanate [Ti (OC then
2H
5)
4], making the original volume volumetric molar concentration of mixing back water is 0.45mol/L, the original volume volumetric molar concentration of tetraethyl titanate is 0.11mol/L, reacts 24 hours down at 45 ℃, obtains white opacity solution, centrifugation again, obtain being with the glossy white precipitate, the vacuum-drying of gained precipitation obtains uniform compound monodispersed nm-class spherical TiO 2 particles, particle diameter promptly clads the titanium dioxide granule of about 55 nanometers of thickness in 555 nanometers.
Embodiment 5
With ammonia, water and positive tetraethyl orthosilicate [Si (OC
2H
5)
4] be added in the etoh solvent, making the original volume volumetric molar concentration of mixing back ammonia is 0.8 mol, the original volume volumetric molar concentration of water is 1.9 mol, the original volume volumetric molar concentration of tetraethyl silicate is 0.22 mol, above-mentioned mixing solutions is at room temperature stirred down reaction 8 hours, obtain turbid solution; With this turbid solution centrifugation, obtain the silicon-dioxide white precipitate then, precipitation of silica with small amount of ethanol washing 2 times, is finally obtained SiO
2Particle, its particle diameter be in 260 nanometers, last SiO
2Particle can leave in the ethanol; Used solvent is recyclable.
20 gram silica dioxide granules are risen in ethanol and acetonitrile (volume ratio 1: the 1) mixing solutions with dispersed with stirring to 1; In above-mentioned mixing solutions, add entry again, add tetraethyl titanate [Ti (OC then
2H
5)
4], the original volume volumetric molar concentration that makes mixed water is 0.1mol/L, the original volume volumetric molar concentration of tetraethyl titanate is 0.02mol/L, reacts 17 hours down at 30 ℃, obtains the oyster white turbid solution, centrifugation again, obtain being with the glossy white precipitate, the vacuum-drying of gained precipitation obtains uniform compound monodispersed nm-class spherical TiO 2 particles, particle diameter promptly clads the titanium dioxide granule of about 70 nanometers of thickness in 330 nanometers.Sintering carries out half an hour at 500 ℃, obtains the titanium dioxide powder of anatase titanium dioxide.
Embodiment 6
Will be by the resulting SiO of preparation among the embodiment 5
2Particle 3 grams are in dispersed with stirring to 200 milliliter ethanol and ethylene glycol (volume ratio 3: 1) mixing solutions; In above-mentioned mixing solutions, add ammoniacal liquor again, add tetrabutyl titanate [Ti (OC then
4H
9)
4], the original volume volumetric molar concentration that makes mixed ammonia is 0.5mol/L, and the original volume volumetric molar concentration of water is 1.6mol/L, and the original volume volumetric molar concentration of tetrabutyl titanate is 0.29mol/L, reacted 48 hours down at 35 ℃, obtain white opacity solution, centrifugation again obtains being with the glossy white precipitate, the vacuum-drying of gained precipitation, obtain uniform compound monodispersed nm-class spherical TiO 2 particles, particle diameter promptly clads the titanium dioxide granule of about 200 nanometers of thickness in 460 nanometers.
Embodiment 7
With ammonia, water and tetraethyl silicate [Si (OC
2H
5)
4] be added drop-wise in the etoh solvent, making the original volume volumetric molar concentration of mixing back ammonia is 8.7 mol, the original volume volumetric molar concentration of water is 19 mol, the original volume volumetric molar concentration of tetraethyl silicate is 1.5 mol, above-mentioned mixing solutions is at room temperature stirred down reaction 20 hours, obtain turbid solution; With this turbid solution centrifugation, obtain the silicon-dioxide white precipitate then, its particle diameter is in 1280 nanometers, last SiO
2Particle can leave in the ethanol; Used solvent is recyclable.
Above-mentioned silica dioxide granule 80 grams are risen in the dehydrated alcohol with dispersed with stirring to 1; In above-mentioned solution, add entry and 25% ammoniacal liquor again, be added dropwise to tetrabutyl titanate [Ti (OC then
4H
9)
4], the original volume volumetric molar concentration that makes mixed ammonia is 0.92mol/L, the original volume volumetric molar concentration of water is 3.0mol/L, and the original volume volumetric molar concentration of tetrabutyl titanate is 0.5mol/L, reacts 36 hours down at 35 ℃, obtain oyster white or white opacity solution, centrifugation again obtains being with the glossy white precipitate, the vacuum-drying of gained precipitation, obtain uniform compound monodispersed nm-class spherical TiO 2 particles, particle diameter is in 1380 nanometers.
Embodiment 8
With ammonia, water and tetraethyl silicate [Si (OC
2H
5)
4] be added in the etoh solvent, making the original volume volumetric molar concentration of mixing back ammonia is 0.5 mol, original volume volumetric molar concentration 2.0 mol of water, the original volume volumetric molar concentration of tetraethyl silicate is 0.18 mol, above-mentioned mixing solutions is at room temperature stirred down reaction 8 hours, obtain the white turbid solution of micro emulsion; SiO
2Particle grain size is in 51 nanometers.
100ml is contained the solution of above-mentioned silica dioxide granule, under agitation add entry again, add tetrabutyl titanate [Ti (OC then
4H
9)
4], the original volume volumetric molar concentration that makes mixed ammonia is 0.5mol/L, the original volume volumetric molar concentration of water is 0.02mol/L, and the original volume volumetric molar concentration of tetrabutyl titanate is 0.0067mol/L/, reacts 12 hours down at 35 ℃, obtain oyster white or white opacity solution, centrifugation again obtains being with the glossy white precipitate, the vacuum-drying of gained precipitation, obtain uniform compound monodispersed nm-class spherical TiO 2 particles, particle diameter is in 70 nanometers.
Claims (5)
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| CN1092147C true CN1092147C (en) | 2002-10-09 |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1296274C (en) * | 2005-03-03 | 2007-01-24 | 武汉理工大学 | Composite microballoon of monodisperse SiO2 and TiO2 and its prepn process |
| CN101319405B (en) * | 2007-06-08 | 2011-05-18 | 中国科学院苏州纳米技术与纳米仿生研究所 | Method for manufacturing TiO2 nanotubes and/or TiO2 nanowhiskers |
| CN101549285B (en) * | 2009-05-13 | 2011-02-02 | 西安理工大学 | A kind of method for preparing nanometer TiO2/SiO2 photocatalytic material |
| CN101913612A (en) * | 2010-09-01 | 2010-12-15 | 中国石油大学(北京) | Preparation method of micron-scale monodisperse silica microspheres |
| CN103351156B (en) * | 2013-07-05 | 2014-07-16 | 陕西师范大学 | Silicon dioxide-based composite ceramic with near-zero resonance frequency temperature coefficient and preparation method thereof |
| CN106492861B (en) * | 2015-09-08 | 2019-02-19 | 中国石油化工股份有限公司 | A kind of catalyst and preparation method thereof being used to prepare cis-butenedioic anhydride |
| CN105768182A (en) * | 2016-04-19 | 2016-07-20 | 滁州卷烟材料厂 | Tobacco flakes added with grape vine and production method tobacco flakes |
| CN108002432A (en) * | 2017-12-14 | 2018-05-08 | 苏州中科纳福材料科技有限公司 | The preparation method of spherical composite material |
| CN114425313B (en) * | 2020-10-14 | 2023-09-29 | 中国石油化工股份有限公司 | Titanium dioxide-aluminum oxide composite oxide and preparation and application thereof |
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