CN101676215B - Method for preparing titanium dioxide nanosphere by using synergistic action of hydrochloric acid and macromolecular compound - Google Patents
Method for preparing titanium dioxide nanosphere by using synergistic action of hydrochloric acid and macromolecular compound Download PDFInfo
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- CN101676215B CN101676215B CN2008102001959A CN200810200195A CN101676215B CN 101676215 B CN101676215 B CN 101676215B CN 2008102001959 A CN2008102001959 A CN 2008102001959A CN 200810200195 A CN200810200195 A CN 200810200195A CN 101676215 B CN101676215 B CN 101676215B
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- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 title claims abstract description 70
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title claims abstract description 40
- 238000000034 method Methods 0.000 title claims abstract description 28
- 239000002077 nanosphere Substances 0.000 title claims abstract description 13
- 239000004408 titanium dioxide Substances 0.000 title claims abstract description 12
- 229920002521 macromolecule Polymers 0.000 title claims abstract description 11
- 230000002195 synergetic effect Effects 0.000 title abstract 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims abstract description 22
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 claims abstract description 16
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims abstract description 11
- 238000003756 stirring Methods 0.000 claims description 22
- 238000002156 mixing Methods 0.000 claims description 13
- 229920000620 organic polymer Polymers 0.000 claims description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- 238000010438 heat treatment Methods 0.000 claims description 8
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 6
- NWZBFJYXRGSRGD-UHFFFAOYSA-M sodium;octadecyl sulfate Chemical compound [Na+].CCCCCCCCCCCCCCCCCCOS([O-])(=O)=O NWZBFJYXRGSRGD-UHFFFAOYSA-M 0.000 claims description 6
- 229960003511 macrogol Drugs 0.000 claims description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 4
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 claims description 2
- 239000004642 Polyimide Substances 0.000 claims description 2
- 150000001408 amides Chemical class 0.000 claims description 2
- 238000001914 filtration Methods 0.000 claims description 2
- 229920000728 polyester Polymers 0.000 claims description 2
- 229920000570 polyether Polymers 0.000 claims description 2
- 229920001721 polyimide Polymers 0.000 claims description 2
- 108090000623 proteins and genes Proteins 0.000 claims description 2
- 102000004169 proteins and genes Human genes 0.000 claims description 2
- 150000003839 salts Chemical class 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims description 2
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims 1
- -1 polyoxyethylene Polymers 0.000 claims 1
- 239000000243 solution Substances 0.000 abstract description 29
- 239000002245 particle Substances 0.000 abstract description 16
- 238000006460 hydrolysis reaction Methods 0.000 abstract description 7
- 238000003837 high-temperature calcination Methods 0.000 abstract description 5
- 230000007062 hydrolysis Effects 0.000 abstract description 5
- 230000008569 process Effects 0.000 abstract description 4
- 239000013078 crystal Substances 0.000 abstract description 2
- 239000002994 raw material Substances 0.000 abstract description 2
- 239000011259 mixed solution Substances 0.000 abstract 2
- 239000002244 precipitate Substances 0.000 abstract 1
- 239000004094 surface-active agent Substances 0.000 abstract 1
- 238000002360 preparation method Methods 0.000 description 23
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 12
- 239000011805 ball Substances 0.000 description 10
- 230000001699 photocatalysis Effects 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 239000002105 nanoparticle Substances 0.000 description 4
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000009792 diffusion process Methods 0.000 description 3
- OUUQCZGPVNCOIJ-UHFFFAOYSA-M Superoxide Chemical compound [O-][O] OUUQCZGPVNCOIJ-UHFFFAOYSA-M 0.000 description 2
- 239000013543 active substance Substances 0.000 description 2
- 239000003945 anionic surfactant Substances 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 239000011807 nanoball Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 241000894006 Bacteria Species 0.000 description 1
- 108010010803 Gelatin Proteins 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000000274 adsorptive effect Effects 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000003115 biocidal effect Effects 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 229920000159 gelatin Polymers 0.000 description 1
- 239000008273 gelatin Substances 0.000 description 1
- 235000019322 gelatine Nutrition 0.000 description 1
- 235000011852 gelatine desserts Nutrition 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000011806 microball Substances 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000006864 oxidative decomposition reaction Methods 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 description 1
- 239000002957 persistent organic pollutant Substances 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- VJZLQIPZNBPASX-OJJGEMKLSA-L prednisolone sodium phosphate Chemical compound [Na+].[Na+].O=C1C=C[C@]2(C)[C@H]3[C@@H](O)C[C@](C)([C@@](CC4)(O)C(=O)COP([O-])([O-])=O)[C@@H]4[C@@H]3CCC2=C1 VJZLQIPZNBPASX-OJJGEMKLSA-L 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 230000005476 size effect Effects 0.000 description 1
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Abstract
The invention relates to a method for preparing a titanium dioxide nanosphere by using synergistic action of hydrochloric acid and a macromolecular compound, which comprises the following steps: (A) dissolving water-soluble organic macromolecules in a 5%-25% hydrochloric acid solution; (B) dripping the mixed solution which is prepared in step A and has the volume which is 1-5 times of the volume of titanium tetrachloride into a titanium tetrachloride solution to obtain brownish-black hydrolyzate; (C) adding a surfactant into the hydrolyzate obtained in step B; and (D) maintaining the temperature of the mixed solution obtained in step C at 50 DEG C-100 DEG C, continuously adding a 5%-25% hydrochloric acid solution according to the volume ratio, and simultaneously adding phosphoric acid. The invention has the advantages that in the process of preparing the titanium dioxide nanosphere, the titanium tetrachloride which is used as a raw material needs to be hydrolyzed under the synergisticaction of the hydrochloric acid and an organic macromolecular substance, and compared with the traditional hydrolysis process, the hydrolysis reaction is moderate, can be controlled easily and can not generate white precipitates easily. Moreover, the prepared nanosphere has no need of high temperature calcination, has complete crystal form and uniform particle diameter, and can be separated and purified easily.
Description
[technical field]
The present invention relates to a kind of method for preparing nanometer ball; Relate in particular to a kind of hydrochloric acid and macromolecular compound synergy utilized; Need not the nanometer anatase titania of high-temperature calcination, preparation 2-8 nanometers, and further be combined to form the preparation method of the nanometer ball of 60-80 nanometers.
[background technology]
Nano titanium oxide is under the irradiation of light; Can produce electronics and hole, generate superoxide radical with being adsorbed on its water or oxygen reaction on every side, this superoxide radical has extremely strong oxidative decomposition capacity; But kill bacteria and decomposing organic pollutant are therefore by the countries in the world common concern.
The photocatalytic activity of nano titanium oxide is directly related with size; One side is along with particle diameter reduces, and quantum size effect that nanoparticle has makes its conduction band and valence-band level become discrete energy levels, and energy gap broadens; The conduction band current potential is more negative; The corrigendum that becomes of valence band current potential, this makes Nano semiconductor particles obtain stronger redox ability, promptly higher photocatalytic activity; Of photoproduction current-carrying diffusion simultaneously also can through simple diffusion from the particle internal migration to particle surface and with electron donor(ED) or electron acceptor(EA) generation oxidation or reduction reaction; Therefore particle diameter reduces; The minimizing significantly of current carrier diffusion time; The separating effect of electric charge strengthens, thereby causes increasing substantially of photocatalytic activity.Nanoparticle reduces on the other hand, and the specific surface area of particle increases, and the specific surface effect also strengthens, and absorption property strengthens.
Therefore preparation is than small particle size; Especially particle diameter is the desirable approach that improve photocatalytic activity less than the nano titanium oxide of 10 nanometers; But the nano titanium oxide of preparation small particle size exists again and separates the difficulty of purifying; Therefore need to seek the reasonable method preparation and can keep the highlight catalytic active of small particle size nano titanium oxide again can be in the preparation process, nano titanium oxide be realized easily separating and is purified.
One Chinese patent application: CN101100311A discloses a kind of preparation method of nano titanium oxide.One Chinese patent application: CN1846849A discloses a kind of preparation method who is used for the photocatalytic microball of environmental treatment.But, also do not appear in the newspapers at present about utilizing hydrochloric acid and macromolecular compound synergy, need not the method that high-temperature calcination prepares titanium dioxide nano-sphere.
[summary of the invention]
The objective of the invention is, provide a kind of hydrochloric acid, macromolecular compound synergy utilized to need not high-temperature calcination, the anatase titanium dioxide of preparation, combination 2-8 nanometers becomes the method for the nanometer ball of 60-80 nanometers.
For realizing above-mentioned purpose, the technical scheme that the present invention takes is:
A kind of method of utilizing hydrochloric acid and macromolecular compound synergy to prepare titanium dioxide nano-sphere, this method may further comprise the steps:
A, water soluble organic polymer is dissolved in 5%-25% the hydrochloric acid soln;
B, with the mixing solutions of steps A configuration by volume 1-5 times of minims to titanium tetrachloride add to the hydrolyzed solution that obtains brownish black in the titanium tetrachloride solution;
C, tensio-active agent is added in the hydrolyzed solution of step B, 10 ℃-95 ℃ of holding temperatures, stirring velocity be at 150 rev/mins-350 rev/mins, stirring heating 2-8 hours;
D, with 50 ℃-100 ℃ of step C mixing solutions holding temperatures, continue by volume, add 5%-20% hydrochloric acid soln, the add-on of hydrochloric acid soln is 0.5-1.5 times of titanium tetrachloride; Add phosphoric acid simultaneously, the add-on of phosphoric acid is 0.1%-3% of a titanium tetrachloride, stirs 0.5-3 hours, and filtration, washing or alcohol are washed, drying.
Water soluble organic polymer described in the steps A is selected from the mixing of polymeric amide, polyimide, poly carboxylic acid, polyester, polyalkenyl alcohol, ROHM or their salt and urethane, polyethers, gelatin, one or more materials of protein.
Water soluble organic polymer described in the steps A is selected from Macrogol 2000.
The weight ratio of water soluble organic polymer and hydrochloric acid soln is 0.5%-3.5% in the steps A.
The weight ratio of water soluble organic polymer and hydrochloric acid soln is 1.1% in the steps A.
The described tensio-active agent of step C is an anionic surfactant.
Said anionic surfactant is a sodium stearyl sulfate.
Holding temperature is 85 ℃ among the step C, and stirring velocity is at 300 rev/mins, stirring heating 4 hours.
The concentration of said hydrochloric acid soln is 20%.
The invention has the advantages that:
1, the present invention is in preparation titanium dioxide nano-sphere process; The raw material titanium tetrachloride needs the synergy at hydrochloric acid and organic polymer material, is hydrolyzed, and hydrolysis reaction is compared with traditional hydrolysis process; Reaction temperature and, easily control, and be difficult for producing white depositions.
2, hydrolyzed solution heats further hydrolysis through a certain proportion of hydrochloric acid and phosphoric acid, can prepare the uniform titanium dioxide nano-sphere of particle diameter, compared with prior art technology simple, need not that high-temperature calcination, energy consumption reduce, reaction is easy to control
3, by the nanometer ball of the inventive method preparation, nano titanium dioxide crystal form is grown complete, and nanometer ball is even, can utilize simple separating device, separates from the mixed system of reaction like, plate and frame(type)filter press, with nanometer ball and purifies.Thereby solved the difficult problem that the nano titanium oxide preparation separates and is prone to run off.
4, by the nanometer ball of the inventive method preparation through antibiotic and degradation of formaldehyde evidence, it all has stronger photocatalytic activity in ultraviolet, visible-range.
5, the nanometer ball by the inventive method preparation has bigger specific surface area, and stronger adsorptive power is through testing its specific surface area greater than 210m
2/ g.
[description of drawings]
Fig. 1 be embodiment 1 preparation be the transmission electron microscope photo that the titanium oxide of 2-8 nanometers is combined to form the titanium dioxide nano-sphere of 60-80 nanometers by particle diameter.
[embodiment]
Below in conjunction with accompanying drawing a kind of embodiment of utilizing hydrochloric acid and macromolecular compound synergy to prepare the method for titanium dioxide nano-sphere provided by the invention is elaborated.
Embodiment 1
One, 15 gram Macrogol 2000s is dissolved in 1200 milliliters 20% hydrochloric acid soln;
Two, the mixing solutions of step 1 configuration is dropped to the hydrolyzed solution that obtains brownish black in 700 milliliters the titanium tetrachloride solution;
Three, the sodium stearyl sulfate with 2 grams adds in the hydrolyzed solution of step 2, and 85 ℃ of holding temperatures are kept 300 rev/mins of stirring velocitys, stirring heating 4 hours;
Four, the step 3 mixing solutions is heated to 95 ℃ and keep this temperature, continues to add 800 milliliter 20% hydrochloric acid soln, add 12 milliliters of phosphoric acid simultaneously, stirs after 1 hour, cooling, filter, wash, get product after the drying and see Fig. 1.Fig. 1 be present embodiment preparation be the transmission electron microscope photo that the titanium oxide of 2-8 nanometers is combined to form the titanium dioxide nano-sphere of 60-80 nanometers by particle diameter.
Embodiment 2
One, 15 gram ZX-Is is dissolved in 3000 milliliters 10% hydrochloric acid soln;
Two, the mixing solutions of step 1 configuration is dropped to the hydrolyzed solution that obtains brownish black in 600 milliliters the titanium tetrachloride solution;
Three, the sodium stearyl sulfate with 2 grams adds in the hydrolyzed solution of step 2, and 95 ℃ of holding temperatures are kept 350 rev/mins of stirring velocitys, stirring heating 8 hours;
Four, the step 3 mixing solutions is heated to 100 ℃ and keep this temperature, continues to add 900 milliliter 10% hydrochloric acid soln, add 18 milliliters of phosphoric acid simultaneously, stirs after 3 hours, cooling, filter, wash, get product after the drying.
Embodiment 3
One, 15 gram Macrogol 2000s and ZX-Is is dissolved in 428 milliliters 25% hydrochloric acid soln;
Two, the mixing solutions of step 1 configuration is dropped to the hydrolyzed solution that obtains brownish black in 428 milliliters the titanium tetrachloride solution;
Three, the sodium stearyl sulfate with 2 grams adds in the hydrolyzed solution of step 2, and 10 ℃ of holding temperatures are kept 180 rev/mins of stirring velocitys, stirring heating 2 hours;
Four, the step 3 mixing solutions is heated to 50 ℃ and keep this temperature, continues to add 214 milliliter 25% hydrochloric acid soln, add 5 milliliters of phosphoric acid simultaneously, stirs after 0.5 hour, cooling, filter, wash, get product after the drying.
Embodiment 4
One, 15 gram Macrogol 2000s is dissolved in 750 milliliters 18% hydrochloric acid soln;
Two, the mixing solutions of step 1 configuration is dropped to the hydrolyzed solution that obtains brownish black in 350 milliliters the titanium tetrachloride solution;
Three, the sodium stearyl sulfate with 3 grams adds in the hydrolyzed solution of step 2, and 70 ℃ of holding temperatures are kept 200 rev/mins of stirring velocitys, stirring heating 3 hours;
Four, the step 3 mixing solutions is heated to 70 ℃ and keep this temperature, continues to add 350 milliliter 18% hydrochloric acid soln, add 1 milliliter of phosphoric acid simultaneously, stirs after 2 hours, cooling, filter, wash, get product after the drying.
Comparative Examples 1
The embodiment of the invention 1: the contrast of preparation titanium oxide method various performance parameters sees the following form 1 in the preparation method of photo-catalytic nano ball and the prior art
Table 1
| Performance | The embodiment of the invention 1: the preparation method of photo-catalytic nano ball | Preparation titanium oxide method (CN1891335A) in the prior art |
| In the preparation to environment requirement | The secondary hydrolysis is carried out in the strength hydrochloric acid environment, and need add phosphoric acid when adding thermal crystalline and preparing nanometer ball | The secondary hydrolysis is directly with containing high molecular aqueous solution preparation |
| Separate the purification difficulty or ease | Easily | Relatively more difficult, nanoparticle runs off easily |
| Particle diameter | 2-8 combinations of nanoparticles are 60-80 nanometer ball | Particle is inhomogeneous, and single dispersion-s of 2-8 nanometers is arranged, and the coacervate less than 20 nanometers is also arranged. |
| Specific surface area | Greater than 200m 2/ g | Greater than 180m 2/ g |
| Catalytic activity | Higher | Higher |
Embodiment and Comparative Examples each item test performance parameter declaration in the table 1, no matter on single performance, still on over-all properties, preparation method of the present invention is superior to Comparative Examples significantly.
The above only is a preferred implementation of the present invention; Should be pointed out that for those skilled in the art, under the prerequisite that does not break away from the inventive method; Can also make some improvement and replenish, these improvement and replenish and also should be regarded as protection scope of the present invention.
Claims (7)
1. method of utilizing hydrochloric acid and macromolecular compound synergy to prepare titanium dioxide nano-sphere, this method may further comprise the steps:
A, water soluble organic polymer is dissolved in the hydrochloric acid soln of 5%-25%;
B, with the mixing solutions of steps A configuration by volume 1-5 doubly add to the hydrolyzed solution that obtains brownish black in the titanium tetrachloride solution to the minim of titanium tetrachloride;
C, AS is added in the hydrolyzed solution of step B, 10 ℃-95 ℃ of holding temperatures, stirring velocity be at 150 rev/mins-350 rev/mins, stirring heating 2-8 hour;
D, with 50 ℃-100 ℃ of step C mixing solutions holding temperatures, continue by volume, add the hydrochloric acid soln of 5%-25%, the add-on of hydrochloric acid soln be titanium tetrachloride 0.5-1.5 doubly; Add phosphoric acid simultaneously, the add-on of phosphoric acid is the 0.1%-3% of titanium tetrachloride, stirs 0.5-3 hour, and filtration, washing or alcohol are washed, drying;
Water soluble organic polymer described in the steps A is selected from one or more in polymeric amide, polyimide, poly carboxylic acid, polyester, polyalkenyl alcohol or their salt, urethane, polyethers, polyoxyethylene glycol, the protein.
2. method according to claim 1 is characterized in that: the water soluble organic polymer described in the steps A is selected from Macrogol 2000.
3. method according to claim 1 is characterized in that: the weight ratio of water soluble organic polymer and hydrochloric acid soln is 0.5%-3.5% in the steps A.
4. method according to claim 1 is characterized in that: the weight ratio of water soluble organic polymer and hydrochloric acid soln is 1.1% in the steps A.
5. method according to claim 1 is characterized in that: said AS is a sodium stearyl sulfate.
6. method according to claim 1 is characterized in that: holding temperature is 85 ℃ among the step C, and stirring velocity is at 300 rev/mins, stirring heating 4 hours.
7. method according to claim 1 is characterized in that: the concentration of said hydrochloric acid soln is 20%.
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| Application Number | Priority Date | Filing Date | Title |
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| CN2008102001959A CN101676215B (en) | 2008-09-19 | 2008-09-19 | Method for preparing titanium dioxide nanosphere by using synergistic action of hydrochloric acid and macromolecular compound |
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| CN2008102001959A CN101676215B (en) | 2008-09-19 | 2008-09-19 | Method for preparing titanium dioxide nanosphere by using synergistic action of hydrochloric acid and macromolecular compound |
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| CN101676215A CN101676215A (en) | 2010-03-24 |
| CN101676215B true CN101676215B (en) | 2012-11-07 |
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1248550A (en) * | 1999-05-12 | 2000-03-29 | 中国科学院上海硅酸盐研究所 | Process for preparing titanic schorl phase titanium dioxide nanometer crystal under room temp. |
| WO2001012555A2 (en) * | 1999-06-24 | 2001-02-22 | Altair Technologies Inc. | Processing aqueous titanium chloride solutions to ultrafine titanium dioxide |
| CN1764602A (en) * | 2003-03-31 | 2006-04-26 | 东陶机器株式会社 | Surface-modified titanium dioxide fine particles and dispersion comprising the same, and method for producing the same |
| CN101100311A (en) * | 2007-08-07 | 2008-01-09 | 上海师范大学 | Process for preparing nanometer titanium dioxide |
-
2008
- 2008-09-19 CN CN2008102001959A patent/CN101676215B/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1248550A (en) * | 1999-05-12 | 2000-03-29 | 中国科学院上海硅酸盐研究所 | Process for preparing titanic schorl phase titanium dioxide nanometer crystal under room temp. |
| WO2001012555A2 (en) * | 1999-06-24 | 2001-02-22 | Altair Technologies Inc. | Processing aqueous titanium chloride solutions to ultrafine titanium dioxide |
| CN1764602A (en) * | 2003-03-31 | 2006-04-26 | 东陶机器株式会社 | Surface-modified titanium dioxide fine particles and dispersion comprising the same, and method for producing the same |
| CN101100311A (en) * | 2007-08-07 | 2008-01-09 | 上海师范大学 | Process for preparing nanometer titanium dioxide |
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