CN1962459A - Method for preparing modified titanium oxide sol, powder and film - Google Patents
Method for preparing modified titanium oxide sol, powder and film Download PDFInfo
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- CN1962459A CN1962459A CN 200610154975 CN200610154975A CN1962459A CN 1962459 A CN1962459 A CN 1962459A CN 200610154975 CN200610154975 CN 200610154975 CN 200610154975 A CN200610154975 A CN 200610154975A CN 1962459 A CN1962459 A CN 1962459A
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- titanium oxide
- powder
- sol
- oxide sol
- modified titanium
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- 239000000843 powder Substances 0.000 title claims abstract description 25
- 238000000034 method Methods 0.000 title claims abstract description 21
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical class [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 title claims abstract description 20
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 27
- 239000002904 solvent Substances 0.000 claims abstract description 22
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims abstract description 20
- -1 nitrogen-containing compound Chemical class 0.000 claims abstract description 13
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 6
- 230000032683 aging Effects 0.000 claims abstract description 4
- DCKVFVYPWDKYDN-UHFFFAOYSA-L oxygen(2-);titanium(4+);sulfate Chemical compound [O-2].[Ti+4].[O-]S([O-])(=O)=O DCKVFVYPWDKYDN-UHFFFAOYSA-L 0.000 claims abstract description 3
- 229910000348 titanium sulfate Inorganic materials 0.000 claims abstract description 3
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 claims abstract description 3
- 239000010408 film Substances 0.000 claims description 20
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 17
- 230000000802 nitrating effect Effects 0.000 claims description 16
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 12
- 229910052757 nitrogen Inorganic materials 0.000 claims description 12
- 239000008279 sol Substances 0.000 claims description 12
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 10
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 9
- 239000002253 acid Substances 0.000 claims description 9
- 238000007865 diluting Methods 0.000 claims description 9
- 229910052500 inorganic mineral Inorganic materials 0.000 claims description 9
- 239000011707 mineral Substances 0.000 claims description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical group O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 7
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 6
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 6
- 239000010936 titanium Substances 0.000 claims description 6
- 229910021529 ammonia Inorganic materials 0.000 claims description 5
- 229910052719 titanium Inorganic materials 0.000 claims description 5
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 4
- 229960000935 dehydrated alcohol Drugs 0.000 claims description 4
- 239000008367 deionised water Substances 0.000 claims description 4
- 229910021641 deionized water Inorganic materials 0.000 claims description 4
- 239000012153 distilled water Substances 0.000 claims description 4
- 230000007062 hydrolysis Effects 0.000 claims description 4
- 238000006460 hydrolysis reaction Methods 0.000 claims description 4
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims description 4
- 239000010409 thin film Substances 0.000 claims description 4
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 3
- 238000013019 agitation Methods 0.000 claims description 3
- 150000001412 amines Chemical class 0.000 claims description 3
- 150000003863 ammonium salts Chemical class 0.000 claims description 3
- 238000000576 coating method Methods 0.000 claims description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-O diazynium Chemical class [NH+]#N IJGRMHOSHXDMSA-UHFFFAOYSA-O 0.000 claims description 3
- 238000003618 dip coating Methods 0.000 claims description 3
- 238000004090 dissolution Methods 0.000 claims description 3
- 230000004048 modification Effects 0.000 claims description 3
- 238000012986 modification Methods 0.000 claims description 3
- 229910017604 nitric acid Inorganic materials 0.000 claims description 3
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 3
- 239000011022 opal Substances 0.000 claims description 3
- 125000001477 organic nitrogen group Chemical group 0.000 claims description 3
- 239000002243 precursor Substances 0.000 claims description 3
- 238000004528 spin coating Methods 0.000 claims description 3
- 238000005507 spraying Methods 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- 239000002131 composite material Substances 0.000 abstract description 2
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 abstract 1
- 239000003085 diluting agent Substances 0.000 abstract 1
- 238000001035 drying Methods 0.000 abstract 1
- 230000003301 hydrolyzing effect Effects 0.000 abstract 1
- 230000000694 effects Effects 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 5
- 238000003837 high-temperature calcination Methods 0.000 description 4
- 238000006555 catalytic reaction Methods 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 238000011065 in-situ storage Methods 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 230000001699 photocatalysis Effects 0.000 description 2
- 239000011941 photocatalyst Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229940105325 3-dimethylaminopropylamine Drugs 0.000 description 1
- 235000012538 ammonium bicarbonate Nutrition 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000003115 biocidal effect Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000029087 digestion Effects 0.000 description 1
- IUNMPGNGSSIWFP-UHFFFAOYSA-N dimethylaminopropylamine Chemical compound CN(C)CCCN IUNMPGNGSSIWFP-UHFFFAOYSA-N 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000002957 persistent organic pollutant Substances 0.000 description 1
- 238000007146 photocatalysis Methods 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
Landscapes
- Inorganic Compounds Of Heavy Metals (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a preparing method of modified titanium oxide sol, powder and film, which comprises the following steps: (1) adding at least one titanium tetrachloride, titanium sulfate or butyl titanate in the alcohol diluent; (2) dripping the composite solution in the step (1) into hydrolytic solvent; (3) dissolving nitrogen-containing compound in the sol evenly; (4) stewing the sol; aging until producing blue white transparent sol; (5) drying the sol into dried powder to obtain titanium oxide powder; (6) filming the sol in the step (4) to form titanium oxide film.
Description
Technical field
The present invention relates to the preparation method of titania photocatalyst, more particularly, relate to a kind of method for preparing modified titanium oxide sol, powder and film.
Background technology
Titanium oxide is as a kind of comparatively ideal semiconductor light-catalyst, at the aspects such as environmental treatment of storage of solar energy and utilization, photochemistry conversion, organic pollutant good application prospects arranged.As add the titania photocatalyst powder in the glaze of pottery, the goods of gained just can possess antibiotic and self-cleaning effect.
Pure zirconia titanium energy gap is bigger, must just can excite by ultraviolet light, and light utilization efficiency is lower.Many researchers is passed through wet chemical technology, in solution, introduce various ions (comprising metal ion and nonmetallic ions such as N, C such as Fe, La),, make metal or nonmetallic ion enter the lattice of titanium oxide by follow-up high-temperature calcination, the position that replaces Ti or O, the energy band structure of change titanium oxide.Like this, titanium oxide can be generalized to the part visible region to the scope of utilizing of light.But the high-temperature calcination in the above-mentioned technology has limited the application mode of titanium oxide, and it can only be occurred with the form of film or powder, and the field (as the body of wall of buildings) that can't be applied to heat labile base material (as plastics) or be difficult to heat; In addition, high-temperature heat treatment process can make titanium oxide grain grow up, and quantum effect weakens, thereby the photochemical catalysis effect reduces.
Other has research, adopts the protective atmosphere of nitrogen, ammonia, prepares the thin film of titanium oxide of nitrating with CVD, plasma method, but higher to equipment requirements, is difficult to commercial application; Also can adopt nitrogen, protection of ammonia atmosphere to mix to realize nitrogen, but be difficult to adulterated amount, process are controlled the high-temperature calcination process in the above-mentioned wet chemical technology.
The application people is that Zhejiang University, Chinese patent application are number for addressing the method for preparing the titanium oxide sol with photocatalysis performance a kind of normal temperature under in the invention of CN200510061118.6.The anatase crystal that contains growth in situ in the made colloidal sol, so colloidal sol directly possesses photocatalytic activity, avoided the high-temperature heat treatment in the traditional technology.
Summary of the invention
The objective of the invention is to overcome deficiency of the prior art, a kind of method for preparing modified titanium oxide sol, powder and film is provided.
The present invention is achieved by the following technical solutions.
A kind of method for preparing modified titanium oxide sol, powder and film may further comprise the steps:
(1) under agitation condition, in the pure diluting solvent with wherein at least a adding of titanium tetrachloride, titanium sulfate or butyl (tetra) titanate 1～10 times (m/m), stirs;
(2) under 5～95 ℃ of bath temperatures, the mixing solutions of gained in the step (1) is dropwise added in the hydrolysising solvent of 1～500 times (m/m), stirred 0.5～5 hour;
(3) the nitrogenous compound uniform dissolution is gone in the colloidal sol of gained in the step (2);
(4) with still aging 1 hour～15 days of the colloidal sol of step (3) gained, transparent until pearl opal, promptly obtain the titanium oxide sol of original position nitrating modification;
(5) get original position nitrating modified titanium oxide sol in the step (4), dry at normal temperatures or be lower than under 100 ℃ and be dried into powder, obtain the nitrating titanium oxide powder;
(6) get original position nitrating modified titanium oxide sol in the step (4), make and dry at normal temperatures after its film forming or be lower than 100 ℃ of oven dry down, obtain the nitrating thin film of titanium oxide.
As a kind of improvement, described pure diluting solvent is wherein a kind of or wherein at least two kinds combination of dehydrated alcohol, ethylene glycol, Virahol.
As a kind of improvement, described hydrolysising solvent is deionized water or distilled water.
As a kind of improvement, when adding the mixing solutions in the step (1) in the hydrolysising solvent, can add mineral acid control hydrolysis speed, described mineral acid can be wherein a kind of or wherein at least two kinds combination of nitric acid, hydrochloric acid, sulfuric acid, and it is 1～5 that the consumption of mineral acid is controlled at the pH value that makes colloidal sol.
As a kind of improvement, described nitrogenous compound is at least a of organic nitrogen-containing presomas such as inorganic nitrogenous precursor such as ammonia, ammonium class or amine, nitro class, diazonium class, nitrogen heterocyclic ring class, and the nitrogenous compound consumption is controlled at and makes that the mol ratio of nitrogen element and titanium elements is 0.1～10% in the colloidal sol.
As a kind of improvement, described film forming adopts spraying, dip-coating, spin coating, it is wherein at least a to scrape coating method.
Compared with prior art, the invention has the beneficial effects as follows:
Adopt a kind of method for preparing modified titanium oxide sol, powder and film provided by the invention, doping colloidal sol, powder and the film of its preparation, avoided common high-temperature calcination heat treatment process, realized the nitrogen doping in very easy mode at low temperatures, made final complex sol have enhanced photochemical catalysis effect.
Embodiment
Below describe the present invention by specific embodiment.
A kind of method for preparing modified titanium oxide sol, powder and film in this specific embodiment may further comprise the steps:
(1) under agitation condition, butyl (tetra) titanate is added in the pure diluting solvent of 1～10 times (m/m), stir;
(2) under 5～95 ℃ of bath temperatures, the mixing solutions of gained in the step (1) is dropwise added in the hydrolysising solvent of 1～500 times (m/m), stirred 0.5～5 hour;
(3) the nitrogenous compound uniform dissolution is gone in the colloidal sol of gained in the step (2);
(4) with still aging 1 hour～15 days of the colloidal sol of step (3) gained, transparent until pearl opal, promptly obtain the titanium oxide sol of original position nitrating modification.
(5) get the original position nitrating modified titanium oxide sol of gained in the step (4), dry at normal temperatures or be lower than under 100 ℃ and be dried into powder, obtain the nitrating titanium oxide powder.
(6) get the original position nitrating modified titanium oxide sol of gained in the step (4), dry at normal temperatures after the film forming in some way or be lower than 100 ℃ of oven dry down, obtain the nitrating thin film of titanium oxide.
Described pure diluting solvent is wherein one or more the combination of dehydrated alcohol, ethylene glycol, Virahol.
Described hydrolysising solvent is deionized water or distilled water.
When adding the mixing solutions in the step (1) in the hydrolysising solvent, can add mineral acid control hydrolysis speed, described mineral acid can be wherein a kind of or wherein at least two kinds combination of nitric acid, hydrochloric acid, sulfuric acid, and it is 1～5 that the consumption of mineral acid is controlled at the pH value that makes colloidal sol.
Described nitrogenous compound is at least a of organic nitrogen-containing presomas such as inorganic nitrogenous precursor such as ammonia, ammonium class or amine, nitro class, diazonium class, nitrogen heterocyclic ring class, and the nitrogenous compound consumption is controlled at and makes that the mol ratio of N and Ti is 0.1～10% in the colloidal sol.
Described film forming adopts spraying, dip-coating, spin coating, it is wherein at least a to scrape coating method.
Testing data in the specific embodiment 1～5 sees the following form:
Wherein the amount of pure diluting solvent is meant pure diluting solvent and the mass ratio that adds butyl (tetra) titanate, the amount of hydrolysising solvent is meant the mass ratio of the mixing solutions in the step (1) of hydrolysising solvent and adding, and the amount of nitrogenous compound is meant the total content and the molar percentage that adds the total content of Ti element in the butyl (tetra) titanate of N element in the various nitrogenous compounds that added.
| The specific embodiment sequence number | 1 | 2 | 3 | 4 | 5 |
| Butyl (tetra) titanate | √ | √ | √ | √ | √ |
| Dehydrated alcohol | √ | √ | |||
| Ethylene glycol | √ | √ | |||
| Virahol | √ | ||||
| Deionized water | √ | √ | √ | ||
| Distilled water | √ | √ | |||
| Bicarbonate of ammonia | √ | √ | √ | ||
| The 3-dimethylamino propylamine | √ | √ | √ | √ | |
| The hydrochloric acid croak | √ | √ | |||
| The amount (m/m) of alcohol diluting solvent | 1 | 2.5 | 5.5 | 7.5 | 10 |
| The amount of hydrolysising solvent (m/m) | 1 | 50 | 180 | 360 | 500 |
| Hydrolysis temperature (℃) | 5 | 20 | 45 | 70 | 95 |
| The amount of nitrogenous compound | 0.1 | 0.8 | 3 | 6.8 | 10 |
| Churning time (h) | 0.5 | 1 | 2 | 3.5 | 5 |
| Digestion time | 15d | 10d | 15d | 10d | 15d |
In the complex sol of the present invention, in preparation and the aged process, the anatase crystal of growth in situ is still among constantly growing and improving, therefore the composite modified nitrogenous compound that adds can be progressively growing among the lattice along with anatase crystal, realize the doping effect of oxygen in the nitrogen replacement lattice, make the titanium oxide crystalline can take existing intermediate level out of, so colloidal sol can utilize the more light of wide region, have enhanced photochemical catalysis effect.
At last, it is also to be noted that what more than enumerate only is some specific embodiment of the present invention.Obviously, the invention is not restricted to above examples of implementation, many distortion can also be arranged.All distortion that those of ordinary skill in the art can directly derive or associate from content disclosed by the invention all should be thought protection scope of the present invention.
Claims (6)
1, a kind of method for preparing modified titanium oxide sol, powder and film is characterized in that, may further comprise the steps:
(1) under agitation condition, in the pure diluting solvent with wherein at least a adding of titanium tetrachloride, titanium sulfate or butyl (tetra) titanate 1～10 times (m/m), stirs;
(2) under 5～95 ℃ of bath temperatures, the mixing solutions of gained in the step (1) is dropwise added in the hydrolysising solvent of 1～500 times (m/m), stirred 0.5～5 hour;
(3) the nitrogenous compound uniform dissolution is gone in the colloidal sol of gained in the step (2);
(4) with still aging 1 hour～15 days of the colloidal sol of step (3) gained, transparent until pearl opal, promptly obtain the titanium oxide sol of original position nitrating modification;
(5) get original position nitrating modified titanium oxide sol in the step (4), dry at normal temperatures or be lower than under 100 ℃ and be dried into powder, obtain the nitrating titanium oxide powder;
(6) get original position nitrating modified titanium oxide sol in the step (4), make and dry at normal temperatures after its film forming or be lower than 100 ℃ of oven dry down, obtain the nitrating thin film of titanium oxide.
2, a kind of method for preparing modified titanium oxide sol, powder and film according to claim 1 is characterized in that, described pure diluting solvent is wherein a kind of or wherein at least two kinds combination of dehydrated alcohol, ethylene glycol, Virahol.
3, a kind of method for preparing modified titanium oxide sol, powder and film according to claim 1 is characterized in that, described hydrolysising solvent is deionized water or distilled water.
4, a kind of method for preparing modified titanium oxide sol, powder and film according to claim 1, it is characterized in that, when adding the mixing solutions in the step (1) in the hydrolysising solvent, can add mineral acid control hydrolysis speed, described mineral acid can be wherein a kind of or wherein at least two kinds combination of nitric acid, hydrochloric acid, sulfuric acid, and it is 1～5 that the consumption of mineral acid is controlled at the pH value that makes colloidal sol.
5, a kind of method for preparing modified titanium oxide sol, powder and film according to claim 1, it is characterized in that, described nitrogenous compound is at least a of organic nitrogen-containing presomas such as inorganic nitrogenous precursor such as ammonia, ammonium class or amine, nitro class, diazonium class, nitrogen heterocyclic ring class, and the nitrogenous compound consumption is controlled at and makes that the mol ratio of nitrogen element and titanium elements is 0.1～10% in the colloidal sol.
6, a kind of method for preparing modified titanium oxide sol, powder and film according to claim 1 is characterized in that, described film forming adopts spraying, dip-coating, spin coating, it is wherein at least a to scrape coating method.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200610154975A CN100591619C (en) | 2006-12-01 | 2006-12-01 | Method for preparing modified titanium oxide sol, powder and film |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200610154975A CN100591619C (en) | 2006-12-01 | 2006-12-01 | Method for preparing modified titanium oxide sol, powder and film |
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| Publication Number | Publication Date |
|---|---|
| CN1962459A true CN1962459A (en) | 2007-05-16 |
| CN100591619C CN100591619C (en) | 2010-02-24 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN200610154975A Expired - Fee Related CN100591619C (en) | 2006-12-01 | 2006-12-01 | Method for preparing modified titanium oxide sol, powder and film |
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| CN (1) | CN100591619C (en) |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100438973C (en) * | 2007-09-29 | 2008-12-03 | 中国科学院山西煤炭化学研究所 | Method for preparing TiO2 visible light photocatalyst |
| CN101805019A (en) * | 2010-04-22 | 2010-08-18 | 南京大学 | Synthesis method of N doped hollow TiO2 microspheres |
| CN101830641A (en) * | 2010-04-01 | 2010-09-15 | 付敏恭 | Preparation method of self-assembly nano-crystalline titanium dioxide film |
| CN102167398A (en) * | 2011-03-16 | 2011-08-31 | 奇瑞汽车股份有限公司 | Preparation method of normal-temperature-cured titanium dioxide sol |
| CN103107307A (en) * | 2013-01-31 | 2013-05-15 | 苏州大学 | Water-solution lithium ion battery negative pole material and preparation method thereof |
| CN103464131A (en) * | 2013-09-17 | 2013-12-25 | 叶红 | Titanium oxide film with excellent photocatalytic performance at visible light wave band |
| CN107502259A (en) * | 2017-09-13 | 2017-12-22 | 陈贤尧 | LED encapsulation material that a kind of hardness is high and adhesion strength is excellent and preparation method thereof |
| CN108976927A (en) * | 2018-08-06 | 2018-12-11 | 安徽嘉美工艺品有限公司 | A kind of gulgul suitable for wood artwork |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102580708B (en) * | 2012-01-06 | 2014-04-16 | 上海交通大学 | Method for preparing nitrogen modified titanium dioxide sol with visible-light catalytic activity |
-
2006
- 2006-12-01 CN CN200610154975A patent/CN100591619C/en not_active Expired - Fee Related
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100438973C (en) * | 2007-09-29 | 2008-12-03 | 中国科学院山西煤炭化学研究所 | Method for preparing TiO2 visible light photocatalyst |
| CN101830641A (en) * | 2010-04-01 | 2010-09-15 | 付敏恭 | Preparation method of self-assembly nano-crystalline titanium dioxide film |
| CN101805019A (en) * | 2010-04-22 | 2010-08-18 | 南京大学 | Synthesis method of N doped hollow TiO2 microspheres |
| CN102167398A (en) * | 2011-03-16 | 2011-08-31 | 奇瑞汽车股份有限公司 | Preparation method of normal-temperature-cured titanium dioxide sol |
| CN103107307A (en) * | 2013-01-31 | 2013-05-15 | 苏州大学 | Water-solution lithium ion battery negative pole material and preparation method thereof |
| CN103464131A (en) * | 2013-09-17 | 2013-12-25 | 叶红 | Titanium oxide film with excellent photocatalytic performance at visible light wave band |
| CN103464131B (en) * | 2013-09-17 | 2015-02-04 | 叶红 | Titanium oxide film with excellent photocatalytic performance at visible light wave band |
| CN107502259A (en) * | 2017-09-13 | 2017-12-22 | 陈贤尧 | LED encapsulation material that a kind of hardness is high and adhesion strength is excellent and preparation method thereof |
| CN108976927A (en) * | 2018-08-06 | 2018-12-11 | 安徽嘉美工艺品有限公司 | A kind of gulgul suitable for wood artwork |
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| Publication number | Publication date |
|---|---|
| CN100591619C (en) | 2010-02-24 |
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