CN1312234C - Preparation of titanium dioxide nano water-based coating by alkali peptication process - Google Patents
Preparation of titanium dioxide nano water-based coating by alkali peptication process Download PDFInfo
- Publication number
- CN1312234C CN1312234C CNB2005100121238A CN200510012123A CN1312234C CN 1312234 C CN1312234 C CN 1312234C CN B2005100121238 A CNB2005100121238 A CN B2005100121238A CN 200510012123 A CN200510012123 A CN 200510012123A CN 1312234 C CN1312234 C CN 1312234C
- Authority
- CN
- China
- Prior art keywords
- titanium dioxide
- preparation
- alkali
- peptication
- based coating
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Images
Abstract
The present invention relates to titanium dioxide nanometer water-based paint prepared by an alkali peptization method, particularly to the preparation of titanium dioxide nanophase material. The present invention is characterized in that the present invention comprises: titaniferous inorganic matter or titaniferous organic matter is hydrolyzed to form hydration positive metatitanic acid gelation; the positive metatitanic acid gelation is dispersed in an alkaline solution with certain concentration; peptization and crystallization reaction are carried out by stirring to obtain the titanium dioxide nanometer water-based paint. The titanium dioxide water-based paint prepared by the present invention has the advantages of good crystallization property and easy dispersion; the paint is applied to material surface, and the phenomena of powder drop, film tension fracture, etc. can not occur after the paint is dried. The present invention also has the advantages of simple preparation technology, mild synthesis condition, no environment pollution, convenient industrialized production, etc.
Description
Technical field:
Preparation of titanium dioxide nano water-based coating by alkali peptication process belongs to the nano material preparation technical field, particularly the preparation of titanium dioxide nano material.
Background technology:
TiO
2It is a kind of nontoxic, inexpensive antibiotic and scavenging material of novel inorganic semi-conductor.Belong to I4
1/ amd, P4
2The anatase octahedrite of/mnm spacer and rutile are two kinds of most important crystal formations, belong to tetragonal system.The energy gap of anatase-type titanium oxide is 3.2eV, and when being subjected to wavelength less than the UV-irradiation of 387.5nm, the electronics on the valence band is excited and transits to conduction band, and stays the hole on valence band, and the valence band current potential in hole is about 3.0V (vs.NHE), and it easily and TiO
2The hydroxyl of surface adsorption is in conjunction with forming hydroxyl radical free radical (OH), and this is a kind of atomic group crude substance with strong oxidation capacity that nature exists, and has extremely strong oxidation disinfection effect, the majority of organic pollutants of can thoroughly degrading.Simultaneously most pathogenic micro-organisms are comprised gram-positive microorganism, negative bacterium, green alga, virus (comprising the RNA type) and tumour, titania photocatalyst shows broad-spectrum sterilization.Thereby titanium dioxide has special application in fields such as environmental improvement, purifying air, sterilization and automatically cleanings.
TiO
2Fixedly be a major issue in the application process, be a kind of very convenient and economical and practical use-pattern directly in various varying environments and material surface with coating spray/brushing film forming.The method of existing preparation titanium dioxide water coating mainly contains: organic and inorganic composite algorithm, peptisation and sol-gel method etc.
Chinese patent publication number CN1287144A, CN1287145A and the described method of CN1380369A have overcome the pollution problem of conventional organic solvents paint with the interior exterior wall nano-paint of nano-titanium oxide and water-soluble organic breast lacquer and the preparation of other fillers, but, reduced the catalytic efficiency and the activity of titanium oxide owing to there is organic parcel.Other various utilizations are synthetic crystalline titania and variously organicly cohere the coating (as the photocuring titanium oxide) that solidifying agent is compounded to form and have similar shortcoming and defect.
It is the short-cut method that phase transformation promotor and dispergator prepare high density, high stability and transparent titanium dioxide colloidal sol at low temperatures with mineral acid that CN1295977A discloses a kind of, the concentration of the mineral acid that this method is used is 0.05-2M, therefore the sol paint of gained is strongly-acid, only is adapted at the acid proof material surface and uses.The method that CN1384165A provides also is the peptized acidic method, by adding silicon-dioxide (after the hydrolysis) inorganic adhesive, has improved the film forming properties and the hydrophilicity of coating, but also only has been applicable to acid resisting material.In addition, above-mentioned two kinds of methods are because the peptization temperature is lower, and the extinction blue shift that the titanium dioxide crystal undersized of acquisition (about 5nm) causes has reduced its photo-catalysis capability under visible light.CN1244516A forms method existence and the CN1384165A and the same or analogous problem of CN1295977A of silica-titania composite coating respectively by silicon sol, titanium colloidal sol with the organism presoma (titanic acid ester and silicon ester) of its counterpart mixed hydrolysis under 0-90 ℃, the condition of pH=1-9, and compo that under weak base and low temperature hydrolysis situation, prepares and instability.Other titania coating that utilizes the titanium organism to form by sol-gel method exists same shortcoming with not enough.
Titanium dioxide ceramic paint that publication number 1169447 provides and method for making thereof, it is characterized in that 50-100 ℃ of heating titanium salt solution, handle semi-permeable membranes dialysis, electrodialysis or ion exchange treatment then, so that at least a portion titanium salt hydrolysis and be converted into titanic hydroxide and TiO
2Micelle.This method is owing to hydrolysis at a lower temperature, the TiO of generation
2Micelle is too small, influences its photo-catalysis capability under visible light equally.In addition because the potential of hydrogen of this aqueous paint in the scope of pH2-5, is positioned at the unstable region of silicon sol, thereby often can't with the compound use of inorganic silicon colloidal sol, be difficult to improve film forming intensity and hydrophilicity.
Summary of the invention:
The purpose of this invention is to provide a kind of method for preparing the nano titania water-borne coatings of well-crystallized and stable dispersion at weak base system hydro-thermal peptization.This coating has good visible light catalysis activity, and can with the compound use of industrial widely used silicon sol.Its ultimate principle is that hydration titanic acid is formed the negative electricity micelle by hydroxyl intercalation, dehydration under hydrothermal condition, because the Coulomb repulsion effect forms stable colloid, and part titanyl acyl hydrolase crystallization simultaneously.The molten process of alkaline water hot glue can be expressed as:
[Ti(OH)
4(H
2O)
2]+OH
-[Ti(OH)
5(H
2O)]
-1+H
2O
[Ti(OH)
5(H
2O)]
-1+OH
-[Ti(OH)
6]
-2+H
2O
[Ti(OH)
6]
-2TiO
2+2H
2O＋2OH
-
Present method is characterised in that, contains following steps successively:
1) preparation hydration titanic acid gel:
1.1) titaniferous inorganics is mixed with the aqueous solution of 0.1-1.0M;
1.2) the above-mentioned solution that is mixed with is warming up to 10 ℃-70 ℃;
1.3) to add mineral alkali be as the hydrolytic precipitation agent, the concentration of mineral alkali is 0.5-5M, with solution neutralize neutrality or weakly alkaline, then obtains the hydration titanic acid gel; With the hydration titanic acid gel with deionized water wash to go out decon;
2) hydro-thermal peptization and crystallization:
2.1) above-mentioned titanic acid gel through washing is scattered in the basic solution, the concentration of solution is 10
-5-10
-3M;
2.2) under condition of stirring in 100 ℃ of-250 ℃ of scopes hydro-thermal 2-24 hour, obtain the TiO 2 sol water-borne coatings.
The described the 1.1st) the titaniferous inorganics in the step is one or more the mixture in titanium sulfate, titanyl sulfate, titanium tetrachloride, the ammonium titanium fluoride.The described the 1.3rd) mineral alkali in the step is one or more a mixture of sodium hydroxide, potassium hydroxide, lithium hydroxide, ammoniacal liquor.The described the 2.1st) basic solution in is one or more the mixture in sodium hydroxide, potassium hydroxide, lithium hydroxide, ammoniacal liquor, the thanomin.Described 2.2) Bu hydrothermal temperature scope is preferably 100 ℃～150 ℃.
The method of another kind of preparation of titanium dioxide nano water-based coating by alkali peptication process is characterised in that it contains following steps successively:
1) preparation hydration titanic acid gel:
1.1) titaniferous organism is mixed with the ethanolic soln of 0.1-1.0M;
1.2) the above-mentioned solution that is mixed with is warming up to 10 ℃-70 ℃, and stir, the hydration titanic acid gel obtained;
2) hydro-thermal peptization and crystallization:
2.1) above-mentioned E metatitanic acid gel is scattered in the basic solution, the concentration of solution is 10
-5-10
-3M;
2.2) under condition of stirring in 100-250 ℃ of scope hydro-thermal 2-24 hour, obtain the TiO 2 sol water-borne coatings;
In the second approach, the described the 1.1st) the titaniferous organism in the step is butyl (tetra) titanate or titanium propanolate.The described the 2.1st) basic solution in is one or more the mixture in sodium hydroxide, potassium hydroxide, lithium hydroxide, ammoniacal liquor, the thanomin.Described 2.2) Bu hydrothermal temperature scope is preferably 100 ℃～150 ℃.
Experiment showed, that method proposed by the invention can prepare and has well-crystallized and nano titania water-borne coatings that can stable dispersion, has reached its intended purposes.
Description of drawings:
Fig. 1 is that hydro-thermal peptization temperature is the transmission electron microscope microstructure of the TiO 2 sol of 100 ℃ of preparations, and the photo upper right corner is a selected diffraction.
Fig. 2 is that hydro-thermal peptization temperature is the transmission electron microscope microstructure of the TiO 2 sol of 120 ℃ of preparations.
Fig. 3 is that hydro-thermal peptization temperature is the transmission electron microscope microstructure of the TiO 2 sol of 150 ℃ of preparations.
Fig. 4 is that hydro-thermal peptization temperature is the transmission electron microscope microstructure of the TiO 2 sol of 250 ℃ of preparations.
Fig. 5 is that hydro-thermal peptization temperature is that the little angle of the X ray of TiO 2 sol after glass surface normal temperature is filmed of 100-150-250 ℃ of preparation is plunderred and penetrated diffraction spectra, and as seen from the figure, the product that present method prepares is an anatase titania.
Embodiment:
The step of method proposed by the invention is as follows:
(1) preparation of hydration titanic acid gel
Titaniferous inorganics or organism by hydrolysis, can be formed the hydration titanic acid gel.Titaniferous inorganic salt that the present invention mentions and organic ester can be titanium sulfates, titanyl sulfate, titanium tetrachloride, ammonium titanium fluoride, butyl (tetra) titanate, titanium propanolate.The precursor of these titanium oxide is mixed with the aqueous solution or the ethanolic soln of 0.1-1.0 M, stirs hydrolysis down at 10-70 ℃.For titaniferous inorganic salt, adding mineral alkali is the hydrolytic precipitation agent, with solution neutralize neutrality or weakly alkaline.Precipitation agent of the present invention can be a kind of of sodium hydroxide, potassium hydroxide, lithium hydroxide, ammoniacal liquor or their mixture, and its concentration is at 0.5-5M.And for titaniferous organic ester, can be in the aqueous solution direct hydrolysis.The titanic acid gel that obtains after the titaniferous inorganic salt hydrolysis repeatedly washs removing absorption foreign ion wherein with deionized water, and for obtain after the titaniferous organic ester hydrolysis apart from the metatitanic acid gel owing to do not contain mineral ion, directly peptization processing.
(2) hydro-thermal peptization and crystallization
The titanic acid gel of washes clean is scattered in certain density basic solution again, places sealed reaction vessel under agitation to carry out peptization and crystallization reaction.Peptization alkali of the present invention can be a kind of of sodium hydroxide, potassium hydroxide, lithium hydroxide, ammoniacal liquor, thanomin or their mixture.The concentration of solution is 10
-5-10
-3M, concentration is low excessively, and peptization is not thorough; Excessive concentration then forms titanate, loses photocatalysis performance.The hydrothermal temperature scope is 100-250 ℃, soaking time 2-24 hour.Hydro-thermal peptization temperature is crossed low not dispergation, and the excessive grain of the too high then titanium dioxide of temperature is grown up, and high temperature system pressure build-up is quick simultaneously, is unfavorable for safety in production.Preferred hydrothermal temperature is 100-150 ℃, can obtain the long strip shape titanium oxide grain in this temperature range, and particle diameter is at 10-20nm, and length is at 50-100nm; At 150-250 ℃ of minor axis or square crystal grain that obtains particle diameter at 40-60nm.
(3) the colloid dilution is with stable
The saturating blue TiO 2 sol of white that the hydro-thermal peptization is obtained promptly obtains water-borne coatings of the present invention with the deionized water dilution.For stability and the film forming bonding force that improves coating, can in titanium oxide sol of the present invention, add the organic or inorganic film coalescence aid, for fear of because hot mechanical mismatches causes the drawing crack phenomenon of film, preferentially adopt long strip shape titanium oxide sol simultaneously 100-150 ℃ of preparation.
Further specify embodiments of the present invention and effect with indefiniteness embodiment below.
Embodiment 1:
The 0.1M titanium sulfate is dissolved in 200 ml deionized water, is warmed up to 40 ℃, add the 3M sodium hydroxide solution under the violent stirring situation, regulating pH is 8.Filtered water lavages foreign ion, and it is 10 that the titanic acid gel of filtration washing is scattered in concentration again
1In the M sodium hydroxide lye, under agitation in 100 ℃ of hydro-thermal peptization 24h, obtain homodisperse long strip shape titanium oxide colloid, grain size is 10-20nm, long 200-300nm.As shown in Figure 1.
Embodiment 2:
The 0.5M titanium sulfate is dissolved in 1000 ml deionized water, is warmed up to 70 ℃, add the 0.5M potassium hydroxide solution under the violent stirring situation, regulating pH is 8.Filtered water lavages foreign ion, and it is 10 that the titanic acid gel of filtration washing is scattered in concentration again
4In the M ammoniacal liquor alkali lye, under agitation, obtain homodisperse long strip shape titanium oxide colloid, as shown in Figure 2 in 120 ℃ of hydro-thermal peptization 5h.
Embodiment 3:
With 0.5M titanium sulfate and the slow titration of 0.5M titanium tetrachloride-alcohol mixed solution in 1000 milliliters of deionized waters, 20 ℃ down and add the 5M concentrated ammonia solution under the violent stirring situation and be hydrolyzed, regulator solution is to neutrality.Filtered water eccysis decon ion, it is 10 that the metatitanic acid gel of filtration washing is scattered in concentration again
-5In the M sodium hydroxide lye, under agitation in 150 ℃ of hydro-thermal peptization 3h, obtain homodisperse colloidal tio 2, grain size is 20-30nm, and long 30-60nm is as accompanying drawing 3.Compare with embodiment 2 with embodiment 1, the grain-size chap of titanium oxide colloid is short.
Embodiment 4:
The ethanolic soln of 115 milliliters of butyl (tetra) titanates is directly added 10 under 10 ℃ and violent stirring situation
-3In the M thanomin alkali lye, under agitation in 250 ℃ of hydro-thermal peptization 2h, obtain homodisperse titanium oxide colloid, grain size is 30-50nm, as shown in Figure 3.Compare with embodiment 3 with embodiment 1, embodiment 2, the crystal grain of titanium oxide colloid develops to the tubbiness shape from long strip type.
Embodiment 5:
The titanium oxide sol water-borne coatings of embodiment 1-4 preparation at room temperature is sprayed on respectively in pottery, glass, metal, plastics or the plank substrate, dries naturally or can form the photocatalytic nanometer film drying below 200 ℃.The titanium oxide that the preparation method who provides by the embodiment of the invention forms is anatase structured through X-ray diffraction analysis, as shown in Figure 5.
The water-borne coatings of the method preparation that the present invention proposes has the following advantages:
(1) under thermal and hydric environment, the crystal property of titanium dioxide is good, disperses easily; Can synthesize titanium oxide crystal by the control hydrothermal temperature with different-shape.
(2) this coating is stable at pH=7-10, can be applied to nearly all material surface, and the crystal of this coating is a long strip shape at low temperatures, can not occur dry linting and film drawing crack phenomenon after the drying.
(3) can have excellent matching with industrial widely used weakly alkaline silicon sol, can direct with it composite formation have excellent hydrophilic and film-forming properties;
(4) raw material of coating is easy to get, and technology is simple, the synthesis condition gentleness, and environmentally safe is convenient to suitability for industrialized production.
Claims (9)
1, preparation of titanium dioxide nano water-based coating by alkali peptication process is characterized in that, it contains following steps successively:
1) preparation hydration titanic acid gel:
1.1) titaniferous inorganics is mixed with the aqueous solution of 0.1-1.0M;
1.2) the above-mentioned solution that is mixed with is warming up to 10 ℃-70 ℃;
1.3) to add mineral alkali be as the hydrolytic precipitation agent, the concentration of mineral alkali is 0.5-5M, with solution neutralize neutrality or weakly alkaline, then obtains the hydration titanic acid gel; With the hydration titanic acid gel with deionized water wash to go out decon;
2) hydro-thermal peptization and crystallization:
2.1) above-mentioned titanic acid gel through washing is scattered in the basic solution, the concentration of solution is 10
-5-10
-3M;
2.2) under condition of stirring in 100 ℃ of-250 ℃ of scopes hydro-thermal 2-24 hour, obtain the TiO 2 sol water-borne coatings.
2, preparation of titanium dioxide nano water-based coating by alkali peptication process as claimed in claim 1, it is characterized in that the described the 1.1st) titaniferous inorganics in the step is one or more the mixture in titanium sulfate, titanyl sulfate, titanium tetrachloride, the ammonium titanium fluoride.
3, preparation of titanium dioxide nano water-based coating by alkali peptication process as claimed in claim 1 is characterized in that, the described the 1.3rd) mineral alkali in the step is one or more a mixture of sodium hydroxide, potassium hydroxide, lithium hydroxide, ammoniacal liquor.
4, preparation of titanium dioxide nano water-based coating by alkali peptication process as claimed in claim 1, it is characterized in that the described the 2.1st) in basic solution be one or more mixture in sodium hydroxide, potassium hydroxide, lithium hydroxide, ammoniacal liquor, the thanomin.
5, preparation of titanium dioxide nano water-based coating by alkali peptication process as claimed in claim 1 is characterized in that, described 2.2) the hydrothermal temperature scope in step is preferably 100 ℃～150 ℃.
6, preparation of titanium dioxide nano water-based coating by alkali peptication process is characterized in that, it contains following steps successively:
1) preparation hydration titanic acid gel:
1.1) titaniferous organism is mixed with the ethanolic soln of 0.1-1.0M;
1.2) the above-mentioned solution that is mixed with is warming up to 10 ℃-70 ℃, and stir, the hydration titanic acid gel obtained;
2) hydro-thermal peptization and crystallization:
2.1) above-mentioned titanic acid gel is scattered in the basic solution, the concentration of solution is 10
-5-10
-3M;
2.2) under condition of stirring in 100-250 ℃ of scope hydro-thermal 2-24 hour, obtain the TiO 2 sol water-borne coatings.
7, preparation of titanium dioxide nano water-based coating by alkali peptication process as claimed in claim 6 is characterized in that, the described the 1.1st) the titaniferous organism in the step is butyl (tetra) titanate or titanium propanolate.
8, preparation of titanium dioxide nano water-based coating by alkali peptication process as claimed in claim 6, it is characterized in that the described the 2.1st) in basic solution be one or more mixture in sodium hydroxide, potassium hydroxide, lithium hydroxide, ammoniacal liquor, the thanomin.
9, preparation of titanium dioxide nano water-based coating by alkali peptication process as claimed in claim 6 is characterized in that, described 2.2) the hydrothermal temperature scope in step is preferably 100 ℃～150 ℃.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2005100121238A CN1312234C (en) | 2005-07-08 | 2005-07-08 | Preparation of titanium dioxide nano water-based coating by alkali peptication process |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2005100121238A CN1312234C (en) | 2005-07-08 | 2005-07-08 | Preparation of titanium dioxide nano water-based coating by alkali peptication process |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1709987A CN1709987A (en) | 2005-12-21 |
| CN1312234C true CN1312234C (en) | 2007-04-25 |
Family
ID=35706280
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2005100121238A Expired - Fee Related CN1312234C (en) | 2005-07-08 | 2005-07-08 | Preparation of titanium dioxide nano water-based coating by alkali peptication process |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1312234C (en) |
Families Citing this family (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101348240B (en) * | 2007-07-18 | 2011-09-21 | 中国科学院过程工程研究所 | Sol-solvent-thermal method for synthesizing nanocrystalline oxide powder |
| CN102491647A (en) * | 2011-11-24 | 2012-06-13 | 盐城工学院 | Preparation method for high emissivity thermal insulation filler with core-shell structure |
| TWI498285B (en) * | 2013-07-31 | 2015-09-01 | Nat Univ Tsing Hua | Synthesis method in controlling shape, crystal surface and size of titanium dioxide |
| CN104195534B (en) * | 2014-09-16 | 2019-10-22 | 中国建材国际工程集团有限公司 | The preparation method of the self-cleaning film of titanium dioxide |
| CN106187051B (en) * | 2016-07-12 | 2018-04-24 | 中山市华山高新陶瓷材料有限公司 | Nano titanium dioxide inorganic coating and preparation method thereof |
| CN107325592B (en) * | 2017-05-19 | 2019-06-18 | 山东朱氏药业集团有限公司 | A kind of antiseptic dressing |
| CN107469554A (en) * | 2017-08-22 | 2017-12-15 | 海宁滴滴箱包智能科技有限公司 | A kind of nonloaded silica/titanic oxide composite microsphere except the preparation method of formaldehyde complex fiber material |
| CN108910943B (en) * | 2018-07-24 | 2020-06-23 | 绍兴文理学院 | Low-temperature microwave preparation method of anatase titanium dioxide |
| CN110482600A (en) * | 2019-09-11 | 2019-11-22 | 中南大学 | A method of rutile titanium dioxide powder is prepared by tetrafluoro oxygen titanium acid ammonium |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1295977A (en) * | 2000-12-19 | 2001-05-23 | 中国科学院上海硅酸盐研究所 | Simple method for preparing titanium dioxide collosol |
| CN1491897A (en) * | 2002-10-23 | 2004-04-28 | 中国科学院化学研究所 | Low temperature preparing process for anatase phase nano crystal titanium dioxide of light catalystic activity |
| CN1562767A (en) * | 2004-03-26 | 2005-01-12 | 攀枝花钢铁有限责任公司钢铁研究院 | Method for preparing nano titania with controllable grain size distribution from rutile |
-
2005
- 2005-07-08 CN CNB2005100121238A patent/CN1312234C/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1295977A (en) * | 2000-12-19 | 2001-05-23 | 中国科学院上海硅酸盐研究所 | Simple method for preparing titanium dioxide collosol |
| CN1491897A (en) * | 2002-10-23 | 2004-04-28 | 中国科学院化学研究所 | Low temperature preparing process for anatase phase nano crystal titanium dioxide of light catalystic activity |
| CN1562767A (en) * | 2004-03-26 | 2005-01-12 | 攀枝花钢铁有限责任公司钢铁研究院 | Method for preparing nano titania with controllable grain size distribution from rutile |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1709987A (en) | 2005-12-21 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN1312234C (en) | Preparation of titanium dioxide nano water-based coating by alkali peptication process | |
| CN101306838B (en) | Method for preparing high- stable neutral mixed crystal nanometer TiO2 hydrosol | |
| CN100546915C (en) | A kind of preparation method of anatase-like titanium dioxide nanometer powder | |
| CN102613245B (en) | Preparation method of nano-silica aerogels | |
| CN100445209C (en) | Preparation method of new type nano-titanium dioxide powder | |
| CN104671282B (en) | A kind of preparation method of composite titania material hollow ball | |
| TW201119947A (en) | Stable nano titania sols and a process for their production | |
| CN103113767B (en) | There is the preparation method of the coating varnish of photocatalytic activity | |
| CN101036886A (en) | Application of mesoporous bigger serface titania and zinc oxide | |
| CN105561975A (en) | Preparation method of nanometer mesoporous SiO2/TiO2 photocatalytic composite material doped with metal ions | |
| CN1686823A (en) | Method for preparing anatase type nano-titanium dioxide in high phase-transition temperature and high specific area | |
| CN107522169A (en) | A kind of normal temperature prepares pure organic homogeneous precipitation method of nano-oxide | |
| CN105536757A (en) | Method for preparing high-activity nano-mesoporous SiO2-TiO2 composite photocatalytic material | |
| CN108128803A (en) | A kind of method that water-soluble titanium dioxide nano-particle is prepared using titanium valve as presoma | |
| CN1636879A (en) | Prepn process of nanometer mesoporous TiO2 powder | |
| CN105836796A (en) | Preparation method of bell-type core-shell structured nano-TiO2(at)void(at)SiO2 powder | |
| CN103601239A (en) | Preparation method of anatase and brookite mixed crystal TiO2 nanowire | |
| CN103601237B (en) | Charged anatase titania nanoparticles and low-temperature preparation method thereof | |
| KR100784137B1 (en) | Titanium Dioxide Photocatalyst and Its Coating Method | |
| CN105107504A (en) | Preparing method for photocatalyst/copper oxide compound light photocatalytic material | |
| CN102120611A (en) | Preparation method of rutile type nano titanium dioxide | |
| JP4343335B2 (en) | Titanium oxide coating film forming composition for photocatalyst and process for producing the same | |
| CN110589881A (en) | Preparation method of waxberry-shaped titanium dioxide/silicon dioxide composite structure particles | |
| KR20080093483A (en) | Synthesis method of coating agent for antipollution | |
| CN101805017B (en) | Preparation method of rutile type titanium dioxide nano particle |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20070425 Termination date: 20160708 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |