CN101643242B - Method for preparing composite titanium oxide nanoparticles - Google Patents
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- CN101643242B CN101643242B CN200810012663XA CN200810012663A CN101643242B CN 101643242 B CN101643242 B CN 101643242B CN 200810012663X A CN200810012663X A CN 200810012663XA CN 200810012663 A CN200810012663 A CN 200810012663A CN 101643242 B CN101643242 B CN 101643242B
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Abstract
The invention relates to a method for preparing titanium oxide nanoparticles, in particular to a method for preparing novel rutile-anatase composite titanium oxide nanoparticles and metal-doped rutile-anatase composite titanium oxide nanoparticles by chemical solution method, wherein the particle size and shape of the prepared particles are controllable. In the method, a precursor of titanium and a precursor of a doping metal M are dissolved in an organic solvent, the solution is added with hydrogen peroxide and reacts with the hydrogen peroxide to form a polymer of a metal peroxide complex, the solvent is evaporated, and the polymer is heated to decompose to form a final product. The novel rutile-anatase composite titanium oxide nanoparticles and the metal-doped rutile-anatase composite titanium oxide nanoparticles, which are prepared by the method, can be used in both photocatalysis materials and carriers of supported catalysts.
Description
Technical field
The present invention relates to the preparation method of titanium oxide nanoparticles, specifically prepare the preparation method of novel rutile/anatase type composite titanium oxide nanoparticles and metal-doped rutile/anatase type composite titanium oxide nanoparticles thereof by chemical solution method.
Background technology
The synthetic method of existing titanium oxide nanoparticles, be the preparation method of Japanese ICHINOSE, be that titanium metal or titanium compound are dissolved in generation titanium peroxidation metal complex polymkeric substance in the hydrogen peroxide, alkaline chemical precipitation is a titanium oxyhydroxide then, will be deposited in 100 ℃ of heat dryings at last and generate the anatase titanium dioxide nanoparticle that superoxide is modified.
The preparation method of Japan ICHINOSE is to add the polymkeric substance that hydrogen peroxide generates titanium peroxidation metal complex again after at first the presoma of titanium being become the oxyhydroxide of titanium, further boils drying again and obtains the titanium oxide nanoparticles of Detitanium-ore-type.No matter the preparation method of existing titanium oxide nanoparticles reports there are not the words of particle diameter and pattern regulation and control from disclosed patent or from paper, can infer that its regulation and control to particle diameter and pattern are difficult.
Summary of the invention
The object of the present invention is to provide a kind of preparation method of composite titanium oxide nanoparticles, and the particle diameter of the nanoparticle of gained and pattern can be regulated.The titanium oxide nanoparticles of the present invention preparation not only can be used for photocatalyst material but also can be used for the carrier of loaded catalyst.
For achieving the above object, the technical solution used in the present invention is:
The present invention is that the presoma with titanium is dissolved in the special organic solvent, adds hydrogen peroxide again, and water-bath was boiled more than 4 hours then, heat drying and obtain rutile/anatase type composite titanium oxide nanoparticles.
A kind of preparation method of composite titanium oxide nanoparticles,
1) special titanium metal complex compound presoma is dissolved in the special organic solvent, forms solution;
Described titanium metal complex compound is the titanium-containing compound of solubility in organic solvent such as titanium isopropylate, 2-methylpropanol titanium, titanium tetraisopropylate or tetramethyl alcohol titanium;
Described organic solvent is pure ethers reagent such as diethylene glycol monoethyl ether, ethylene glycol monoethyl ether, diethylene glycol monobutyl ether, terephthaldehyde's ether, a phenylene dimethyl ether or ethylene glycol phenyl ether;
The bulking value concentration that the titanium metal complex compound is dissolved in the organic solvent is 0.15-3g/ml; Water-bath boiling time 〉=4 hour; 100-120 ℃ of heat drying temperature, time 12-24 hour.
2) add hydrogen peroxide in above-mentioned solution, reaction is boiled in water-bath then, the reaction post-heating is dry and obtain rutile/anatase type composite titanium oxide nanoparticles.
Water-bath is boiled reaction back and is added precious metals platinum catalyst, and catalytic decomposition is removed excessive hydrogen peroxide, and then heat drying and obtain rutile/anatase type composite titanium oxide nanoparticles; The concentration of described hydrogen peroxide is 5-90% (volume ratio), and the consumption volume ratio of itself and step 1) gained solution is 3-30.
Also can be added with element M in the described step 1) solution, M is V, Fe, and Ni, Mo, W, Nb, Ta, Sn, Sb or Bi, its doping is 0.001-0.1 for the M/Ti mol ratio; Element M be with its a kind of can making an addition in the step 1) solution by the dissolved compound form in organic solvent, as contains the soluble salt of element M, as: the M complex compound of methyl ethyl diketone and derivative thereof, ethylenediamine tetraacetic acid (EDTA) and related M complex compound thereof etc.
Can carry out further thermal treatment to it after heat drying obtains rutile/anatase type composite titanium oxide nanoparticles, it is 〉=1 hour with the time that thermal treatment temp is 〉=150 ℃.
The present invention and existing preparation method contrast have following characteristics:
But the present invention uses the powder of titanium metal also titania/Detitanium-ore-type composite titanium oxide nanoparticles and metal-doped rutile/anatase type composite titanium oxide nanoparticles thereof.
But use by the present invention and to contain aerobic and protium wherein a kind of presoma also synthesizing new rutile/anatase type composite titanium oxide nanoparticles and metal-doped rutile/anatase type composite titanium oxide nanoparticles thereof of titanium of element at least.
The present invention and Japanese ICHINOSE preparation method's common ground is by adding hydrogen peroxide, the presoma of titanium being become the polymkeric substance of titanium peroxidation metal complex.Polymkeric substance with this titanium peroxidation metal complex boils drying and obtains titanium oxide nanoparticles about 100 ℃ then.
The difference of the present invention and prior art is:
1) the present invention is that presoma with titanium is dissolved in the organic solvent, by adding that hydrogen peroxide boils and the polymkeric substance that directly obtains titanium peroxidation metal complex.Afterwards, add precious metals platinum catalyst, catalytic decomposition is removed excessive hydrogen peroxide, boils the composite titanium oxide nanoparticles that drying obtains the rutile/anatase type then.That is to say that what the present invention directly obtained is the compound phase of rutile/anatase type titanium oxide nanoparticles, but not pure anatase titanium dioxide nanoparticle; And prior preparation method can only obtain the anatase titanium dioxide nanoparticle.
Moreover the present invention also can prepare metal-doped rutile/anatase type composite titanium oxide nanoparticles by the presoma that adds other metal.And in photochemical catalysis research, by metal-doped, such as the doping of known iron, tungsten, bismuth etc. can make titanium oxide nanoparticles that visible light is had responsiveness, thereby improve its photocatalysis efficiency, realizes the effective utilization to sun power.
2) simultaneously, the present invention just can realize making the particle diameter and the pattern of driving composite titanium oxide nanoparticles by regulating volume of organic solvent and metal doping amount, and what reach that general preparation method is difficult to realize carries out the requirement that nano level is regulated and control to particulate.
By the presoma of adjusting titanium and the particle diameter and the pattern of volume of organic solvent consumption may command rutile/anatase type composite titanium oxide nanoparticles.Promptly compare with existing preparation method, chemical solution preparation method of the present invention can be imperial to the particle diameter and the pattern system of titanium oxide nanoparticles.
When controlling the particle diameter of metal-doped rutile/anatase type composite titanium oxide nanoparticles and pattern, both can also can realize by presoma and the volume of organic solvent consumption of regulating titanium by regulating the metal doping amount.
3) particle diameter of the rutile/anatase type composite titanium oxide nanoparticles that obtains of the present invention and metal-doped rutile/anatase type composite titanium oxide nanoparticles thereof is even, degree of crystallinity is high, can say to have special pattern.
4) the metal-doped amount of the metal-doped titanium oxide nanoparticles of the present invention preparation is obviously greater than the metal-doped titanium oxide nanoparticles with the preparation of methods such as collosol and gel, co-precipitation of bibliographical information.Such as under the adulterated situation of iron, so far, the maximum doping of the bibliographical information that can find is about 6.5% (molecular fraction), and this preparation method can make the doping of iron reach 10% (molecular fraction) at least.
Description of drawings
Fig. 1 is the powder X-ray ray diffraction diagram of novel rutile/anatase type composite titanium dioxide and iron doped rutile/Detitanium-ore-type composite titanium oxide nanoparticles thereof.The Novel Titanium dioxide nanoparticle of the chemical solution method preparation of last note was exactly the coexistence of rutile/anatase crystallization phases before iron mixes, and mixed by iron, and the rutile-type crystalline phase tails off, and the Detitanium-ore-type crystalline phase increases.
Fig. 2 is the UV-vis diffused reflection spectrum of novel rutile/anatase type composite titanium dioxide and iron doped rutile/Detitanium-ore-type composite titanium oxide nanoparticles.Can be clear that iron has had obvious absorption in the visible absorption field after mixing.Compose as can be seen from powder X-ray ray diffraction diagram and UV-vis diffused reflection, two effects have been played in the doping of iron: the one, increase the Detitanium-ore-type crystalline phase; The 2nd, make titanium oxide nanoparticles obvious absorption arranged to visible light.
Fig. 3 is 500 ℃, the novel rutile/anatase type composite titanium oxide nanoparticles after 2 hours heat treated and the powder X-ray ray diffraction diagram of iron doped rutile/Detitanium-ore-type composite titanium oxide nanoparticles.As can be seen by thermal treatment, rutile/anatase type composite phase titanic oxide nanoparticle is converted into the rutile-type crystalline phase mostly, and the degree of crystallinity of iron doped rutile/Detitanium-ore-type composite titanium oxide nanoparticles improves, the ratio showed increased of rutile-type crystalline phase.
Fig. 4 is new sections doped rutile/Detitanium-ore-type composite titanium oxide nanoparticles typical case at room temperature
57The Fe Mo﹠4﹠ssbauer spectrum.When the Mo﹠4﹠ssbauer spectrum result shows the doping x=1% (molar percentage, down with) of iron, iron only be present in the little rutile of structural distortion mutually in; X=2% and 5% o'clock, iron both be present in the little rutile of structural distortion mutually in, also be present in the big relatively anatase octahedrite of structural distortion mutually in; During x=10%, iron-based originally all enter the big relatively anatase octahedrite of structural distortion mutually in.
Fig. 5 is the typical transmission electron microscope photo of novel rutile/anatase type composite titanium dioxide and iron doped rutile/Detitanium-ore-type composite titanium oxide nanoparticles.Can see that nanoparticle all has good degree of crystallinity, and pattern is the ellipsoid shape.Concerning each sample, particle diameter is all basic identical.Particle diameter is not bigger when having iron to mix, and is about 40 nanometers, and particle diameter obviously diminishes when having iron to mix.During doping x=1%, particle diameter is about 8 nanometers, and along with the increase of doping, particle diameter has the trend of increase subsequently, but when the x=5%, particle diameter is all less than 40 nanometers.The doping that is iron can suppress growing up of titanium oxide nanoparticles again, that is to say, just can make the particle diameter and the pattern of driving titanium oxide nanoparticles by the doping of regulating iron.
Embodiment
One, novel rutile/anatase type composite titanium oxide nanoparticles
Embodiment 1
The preparation of rutile/anatase type composite titanium oxide nanoparticles: in the beaker that 2.7 gram titanium isopropylates addings are 500 milliliters, add 10 milliliters of ethylene glycol monoethyl ether organic solvents again.Afterwards, when stirring, add 30 milliliter of 45% hydrogen peroxide.Keep when stirring, this mixing solutions is put into water-bath boiled 4 hours.In order to prevent solution evaporation, to add a cover furnace pot on the beaker when boiling.Afterwards, several metal platinum catalyzer are joined in the mixing solutions, the decomposing hydrogen dioxide solution of surplus is removed.Then again with solution evaporate to dryness lentamente, the residuum that obtains can obtain the novel rutile/anatase type composite titanium oxide nanoparticles of the even high-crystallinity of particle diameter in 24 hours 120 ℃ of dryings.
With powder X-ray line diffraction analysis has been done in the crystalline phase variation before and after crystalline phase, purity and the thermal treatment of gained nanoparticle, with UV, visible light diffused reflection the photo absorption performance of gained nanoparticle has been done analysis, the particle diameter and the monodispersity of gained nanoparticle have been done observation with transmission electron microscope.Result such as Fig. 1,2,3, shown in 5.
Embodiment 2
The preparation of the novel rutile/anatase type composite titanium oxide nanoparticles of different-grain diameter and pattern: in the different beakers with 500 milliliters of the pure titanium addings of 2-methylpropanol titanium, titanium tetraisopropylate, the tetramethyl of 2.7 grams, add 10 milliliters of ethylene glycol monoethyl ether organic solvents more respectively.Afterwards, operation steps is identical with embodiment 1, can obtain the novel rutile/anatase type composite titanium oxide nanoparticles of three kinds of different-grain diameters and pattern.Identical with embodiment 1, with powder X-ray line diffraction, UV, visible light diffused reflection and transmission electron microscope etc. the gained nanoparticle has been made sign respectively.The result shows that the presoma of different titaniums can obviously influence the particle diameter and rutile/anatase mol ratio mutually of titanium oxide nanoparticles.Result such as Fig. 1,2,3, shown in 5.
Embodiment 3
The preparation of the novel rutile/anatase type composite titanium oxide nanoparticles of different-grain diameter and pattern: four part of 2.7 gram titanium isopropylate added respectively in 500 ml beakers, add 5,20,30,40 milliliters of ethylene glycol monoethyl ether organic solvents more respectively.Afterwards, operation steps is identical with embodiment 1, can obtain the novel rutile/anatase type composite titanium oxide nanoparticles of different-grain diameter and pattern.Identical with embodiment 1, with powder X-ray line diffraction, UV, visible light diffused reflection and transmission electron microscope etc. the gained nanoparticle has been made sign respectively.The result shows that the ethylene glycol monoethyl ether volume of organic solvent can obviously influence particle diameter, dispersity and the rutile/anatase mol ratio mutually of titanium oxide nanoparticles.Result such as Fig. 1,2,3, shown in 5.
Embodiment 4
The preparation of the novel rutile/anatase type composite titanium oxide nanoparticles of different-grain diameter and pattern: five part of 2.7 gram titanium isopropylate added respectively in 500 ml beakers, add 10 milliliters of diethylene glycol monoethyl ethers, diethylene glycol monobutyl ether, terephthaldehyde's ether, a phenylene dimethyl ether, ethylene glycol phenyl ether organic solvent more respectively.Afterwards, operation steps is identical with embodiment 1, can obtain the novel rutile/anatase type composite titanium oxide nanoparticles of different-grain diameter and pattern.Identical with embodiment 1, with powder X-ray line diffraction, UV, visible light diffused reflection and transmission electron microscope etc. the gained nanoparticle has been made sign respectively.The result shows that the kind of organic solvent can obviously influence the particle diameter and rutile/anatase mol ratio mutually of titanium oxide nanoparticles equally.Result such as Fig. 1,2,3, shown in 4,5.
Two, novel metal doped rutile/anatase type composite titanium oxide nanoparticles
Embodiment 1
Iron doped rutile/Detitanium-ore-type composite titanium oxide nanoparticles: 4 part of 1.7 gram titanium isopropylate added respectively in 500 ml beakers, add 10 milliliters of ethylene glycol monoethyl ether organic solvents again, this mixing solutions is named and is solution I-1, I-2, I-3, I-4.
Weighing 0.02 respectively, 0.05,0.11,0.23g iron acetylacetonate complex (being methyl ethyl diketone complexing iron) add in 50 milliliters of vials with cover, add 10 milliliters of ethylene glycol monoethyl ether organic solvents afterwards respectively, fully shake up to the iron acetylacetonate complex and dissolve fully, this mixing solutions named be solution II-1, II-2, II-3, II-4.
Afterwards, in continuous stirred solution I, respectively solution II is joined in the solution I lentamente.When continue stirring, join 30 milliliters in 45% hydrogen peroxide in the mixing solutions after, this mixing solutions water-bath was boiled 4 hours.45% hydrogen peroxide has just added fashionable, reacts very violent.In order to prevent that solution from splashing, can add a certain amount of pure water in mixing solutions.When water-bath is boiled,, a furnace pot can be covered on beaker in order to prevent the evaporation of solution.After 4 hours the heated and boiled, 3 small pieces metal platinum catalyzer are added mixing solutions, catalytic decomposition is removed superfluous hydrogen peroxide.Then respectively with solution evaporate to dryness lentamente, the residuum that obtains can obtain the new sections doped rutile/Detitanium-ore-type composite titanium oxide nanoparticles of the even high-crystallinity of particle diameter in 24 hours 120 ℃ of dryings.With powder X-ray line diffraction analysis has been done in the crystalline phase variation before and after crystalline phase, purity and the thermal treatment of gained nanoparticle, the photo absorption performance of gained nanoparticle has been done analysis, used with UV, visible light diffused reflection
57The Fe Mo﹠4﹠ssbauer spectrum has been done analysis to the existence of the iron of gained nanoparticle, with transmission electron microscope the particle diameter and the monodispersity of gained nanoparticle has been done observation.The result clearly shows, the doping of iron can influence the mole photo absorption performance when of particle diameter, the rutile/anatase phase of titanium oxide nanoparticles.After iron mixed, titanium oxide nanoparticles had had absorption significantly at visible-range.
The degree of crystallinity of the new sections doped rutile/Detitanium-ore-type composite titanium oxide nanoparticles of gained was become better in 2 hours 500 ℃ of heating, can regulate the mol ratio of rutile/anatase crystalline phase simultaneously.Same with powder X-ray line diffraction, UV, visible light diffused reflection,
57Fe Mo﹠4﹠ssbauer spectrum and transmission electron microscope etc. to the work of gained nanoparticle sign.Result such as Fig. 1,2,3, shown in 4,5.
Embodiment 2
Tungsten doped rutile/Detitanium-ore-type composite titanium oxide nanoparticles: it is tungsten acetylacetonate complex (being methyl ethyl diketone complexing tungsten) that the iron acetylacetonate complex among the embodiment 1 is changed, and just can synthesize the novel tungsten doped rutile/Detitanium-ore-type composite titanium oxide nanoparticles of the even high-crystallinity of particle diameter.Change with the crystalline phase of powder X-ray line diffraction after and to have done analysis crystalline phase, purity and the thermal treatment of gained nanoparticle, with UV, visible light diffused reflection the photo absorption performance of gained nanoparticle has been done analysis, the particle diameter and the monodispersity of gained nanoparticle have been done observation with transmission electron microscope.
The degree of crystallinity of the novel tungsten doped rutile/Detitanium-ore-type composite titanium oxide nanoparticles of gained was become better in 2 hours 500 ℃ of heating, can regulate the mol ratio of rutile/anatase crystalline phase simultaneously.Same with powder X-ray line diffraction, UV, visible light diffused reflection and transmission electron microscope etc. to the work of gained nanoparticle sign.
Embodiment 3
The preparation of the iron doped rutile/Detitanium-ore-type composite titanium oxide nanoparticles of different-grain diameter and pattern: it is 2-methylpropanol titanium or titanium tetraisopropylate or the pure titanium of tetramethyl that the titanium isopropylate among the embodiment 1 can be changed, the organic solvent ethylene glycol monoethyl ether can change and be diethylene glycol monoethyl ether or diethylene glycol monobutyl ether or terephthaldehyde's ether or a phenylene dimethyl ether or ethylene glycol phenyl ether, and it is 5 or 20 or 30 or 40 milliliters that volume of organic solvent can be changed by 10 milliliters.Other condition is constant, more than three condition changings one of them just can synthesize the iron doped rutile/Detitanium-ore-type composite titanium oxide nanoparticles of different-grain diameter and pattern.Same with powder X-ray line diffraction, UV, visible light diffused reflection,
57Fe Mo﹠4﹠ssbauer spectrum and transmission electron microscope etc. to the work of gained nanoparticle sign.Result such as Fig. 1,2,3, shown in 4,5.
Embodiment 4
The preparation of the tungsten doped rutile/Detitanium-ore-type composite titanium oxide nanoparticles of different-grain diameter and pattern: it is 2-methylpropanol titanium or titanium tetraisopropylate or the pure titanium of tetramethyl that the titanium isopropylate among the embodiment 2 can be changed, the organic solvent ethylene glycol monoethyl ether can change and be diethylene glycol monoethyl ether or diethylene glycol monobutyl ether or terephthaldehyde's ether or a phenylene dimethyl ether or ethylene glycol phenyl ether, and it is 5 or 20 or 30 or 40 milliliters that volume of organic solvent can be changed by 10 milliliters.Other condition is constant, more than three condition changings one of them just can synthesize the tungsten doped rutile/Detitanium-ore-type composite titanium oxide nanoparticles of different-grain diameter and pattern.Same with powder X-ray line diffraction, UV, visible light diffused reflection and transmission electron microscope etc. to the work of gained nanoparticle sign.
Claims (6)
1. the preparation method of a composite titanium oxide nanoparticles is characterized in that:
1) titanium metal complex compound presoma is dissolved in the organic solvent, forms solution;
2) add hydrogen peroxide in above-mentioned solution, reaction is boiled in water-bath then, the reaction post-heating is dry and obtain rutile/anatase type composite titanium oxide nanoparticles;
Wherein: described titanium metal complex compound is titanium isopropylate, 2-methylpropanol titanium, titanium tetraisopropylate or tetramethyl alcohol titanium; Described organic solvent is diethylene glycol monoethyl ether, ethylene glycol monoethyl ether, diethylene glycol monobutyl ether, terephthaldehyde's ether, a phenylene dimethyl ether or ethylene glycol phenyl ether; The bulking value concentration that the titanium metal complex compound is dissolved in the organic solvent is 0.15-3g/ml; Water-bath boiling time 〉=4 hour;
Boil reaction back in water-bath and add precious metals platinum catalyst in solution, catalytic decomposition is removed excessive hydrogen peroxide, and then heat drying and obtain rutile/anatase type composite titanium oxide nanoparticles.
2. according to the described preparation method of claim 1, it is characterized in that:
The concentration of described hydrogen peroxide is 5-90% (volume ratio), and the consumption volume ratio of itself and step 1) gained solution is 3-30.
3. according to the described preparation method of claim 1, it is characterized in that:
Also contain element M in the described step 1) solution, M is V, Fe, and Ni, Mo, W, Nb, Ta, Sn, Sb or Bi, its doping is 0.001-0.1 for the M/Ti mol ratio.
4. according to the described preparation method of claim 3, it is characterized in that: described element M is with its a kind of can making an addition in the step 1) solution by the dissolved compound form in organic solvent.
5. according to the described preparation method of claim 1, it is characterized in that: it is 12-24 hour with the time that the heat drying temperature is 100-120 ℃.
6. according to the described preparation method of claim 1, it is characterized in that: can carry out further thermal treatment to it after heat drying obtains rutile/anatase type composite titanium oxide nanoparticles, it is 〉=1 hour with the time that thermal treatment temp is 〉=150 ℃.
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| CN103521204A (en) * | 2012-07-06 | 2014-01-22 | 中国科学院大连化学物理研究所 | Preparation method of strong adsorptive mixed crystal titanium dioxide |
| PT106550B (en) * | 2012-09-27 | 2014-11-05 | Ntio2 Lda | NON-ESTEQUIOMETRIC TITANIUM OXIDE SHOWING IMPROVED PHOTOCATALYTIC AND ANTI-BACTERIAL PROPERTIES, PROCESS FOR PREPARING AND USING THE SAME |
| CN103861601B (en) * | 2012-12-18 | 2016-03-02 | 中国科学院大连化学物理研究所 | A kind of preparation method of fixing crystalline phase composition different content Fe2O3 doping titanium dioxide |
| CN104248955A (en) * | 2013-06-28 | 2014-12-31 | 中国科学院大连化学物理研究所 | Method for preparing iron-doped rutile titanium dioxide |
| CN103396634B (en) * | 2013-08-13 | 2016-01-13 | 武汉羿阳科技有限公司 | A kind of self-cleaning antibacterial anti-fog thin film |
| CN105702318B (en) * | 2016-03-16 | 2017-11-24 | 山东东佳集团股份有限公司 | The method that dry method doping prepares rutile-type conductive titanium dioxide |
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| US6306361B1 (en) * | 1999-04-23 | 2001-10-23 | Nano Co., Ltd. | Method for manufacturing photocatalytic anatase titanium dioxide powder |
| CN1415550A (en) * | 2002-12-12 | 2003-05-07 | 中山大学 | Method for preparing nano titanium dioxide in anatase type from fluid of hydrothermal crystallized titanium sulfate |
| CN1712357A (en) * | 2004-06-15 | 2005-12-28 | 中国科学院理化技术研究所 | Preparation of single-disperse shperical titanic oxide gel particle with controllable size and appearance |
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| US6306361B1 (en) * | 1999-04-23 | 2001-10-23 | Nano Co., Ltd. | Method for manufacturing photocatalytic anatase titanium dioxide powder |
| CN1415550A (en) * | 2002-12-12 | 2003-05-07 | 中山大学 | Method for preparing nano titanium dioxide in anatase type from fluid of hydrothermal crystallized titanium sulfate |
| CN1712357A (en) * | 2004-06-15 | 2005-12-28 | 中国科学院理化技术研究所 | Preparation of single-disperse shperical titanic oxide gel particle with controllable size and appearance |
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