CN1563490A - Titania thin film possessing high catalytic activity under visible light and preparation method - Google Patents
Titania thin film possessing high catalytic activity under visible light and preparation method Download PDFInfo
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- CN1563490A CN1563490A CN 200410033800 CN200410033800A CN1563490A CN 1563490 A CN1563490 A CN 1563490A CN 200410033800 CN200410033800 CN 200410033800 CN 200410033800 A CN200410033800 A CN 200410033800A CN 1563490 A CN1563490 A CN 1563490A
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- catalytic activity
- visible light
- high catalytic
- under visible
- film
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- 230000003197 catalytic effect Effects 0.000 title claims abstract description 27
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title abstract description 32
- 239000010409 thin film Substances 0.000 title description 7
- 150000003839 salts Chemical class 0.000 claims abstract description 14
- 238000003980 solgel method Methods 0.000 claims abstract description 5
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 22
- 229910052719 titanium Inorganic materials 0.000 claims description 21
- 239000010936 titanium Substances 0.000 claims description 21
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical group Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 14
- 229910003002 lithium salt Inorganic materials 0.000 claims description 13
- 159000000002 lithium salts Chemical class 0.000 claims description 13
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical group CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 12
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- 239000003377 acid catalyst Substances 0.000 claims description 10
- 230000001476 alcoholic effect Effects 0.000 claims description 10
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 claims description 10
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 10
- 239000002904 solvent Substances 0.000 claims description 10
- 239000002253 acid Substances 0.000 claims description 8
- TZMFJUDUGYTVRY-UHFFFAOYSA-N pentane-2,3-dione Chemical group CCC(=O)C(C)=O TZMFJUDUGYTVRY-UHFFFAOYSA-N 0.000 claims description 8
- 238000007669 thermal treatment Methods 0.000 claims description 8
- 239000011159 matrix material Substances 0.000 claims description 7
- FAPDDOBMIUGHIN-UHFFFAOYSA-K antimony trichloride Chemical compound Cl[Sb](Cl)Cl FAPDDOBMIUGHIN-UHFFFAOYSA-K 0.000 claims description 6
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical group [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 claims description 6
- 239000011248 coating agent Substances 0.000 claims description 5
- 238000000576 coating method Methods 0.000 claims description 5
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 claims description 5
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 4
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 4
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 4
- WBJXZTQXFVDYIZ-UHFFFAOYSA-N [Sb].[N+](=O)(O)[O-] Chemical group [Sb].[N+](=O)(O)[O-] WBJXZTQXFVDYIZ-UHFFFAOYSA-N 0.000 claims description 4
- 229910017604 nitric acid Inorganic materials 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 4
- -1 titanic acid ester Chemical class 0.000 claims description 4
- JMXKSZRRTHPKDL-UHFFFAOYSA-N titanium ethoxide Chemical compound [Ti+4].CC[O-].CC[O-].CC[O-].CC[O-] JMXKSZRRTHPKDL-UHFFFAOYSA-N 0.000 claims description 4
- 229960004418 trolamine Drugs 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 3
- 230000005855 radiation Effects 0.000 claims description 3
- 238000000034 method Methods 0.000 abstract description 6
- 238000000354 decomposition reaction Methods 0.000 abstract description 5
- 230000015556 catabolic process Effects 0.000 abstract description 4
- 238000006731 degradation reaction Methods 0.000 abstract description 4
- 229910052787 antimony Inorganic materials 0.000 abstract description 2
- 229910010252 TiO3 Inorganic materials 0.000 abstract 1
- 230000009466 transformation Effects 0.000 abstract 1
- 239000010408 film Substances 0.000 description 33
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 11
- 239000004408 titanium dioxide Substances 0.000 description 7
- 239000000463 material Substances 0.000 description 6
- 239000013078 crystal Substances 0.000 description 4
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 2
- 229910001416 lithium ion Inorganic materials 0.000 description 2
- 239000003973 paint Substances 0.000 description 2
- 229910013553 LiNO Inorganic materials 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- 238000001237 Raman spectrum Methods 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 229910001439 antimony ion Inorganic materials 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005587 bubbling Effects 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 229940125904 compound 1 Drugs 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- STZCRXQWRGQSJD-GEEYTBSJSA-M methyl orange Chemical compound [Na+].C1=CC(N(C)C)=CC=C1\N=N\C1=CC=C(S([O-])(=O)=O)C=C1 STZCRXQWRGQSJD-GEEYTBSJSA-M 0.000 description 1
- 229940012189 methyl orange Drugs 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 230000001699 photocatalysis Effects 0.000 description 1
- 238000007146 photocatalysis Methods 0.000 description 1
- 239000011941 photocatalyst Substances 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000009281 ultraviolet germicidal irradiation Methods 0.000 description 1
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- Catalysts (AREA)
Abstract
This invention discloses a TiO2 film with high light catalytic activity under visible light and its preparation method. Li and Sb salt are added in TiO2 sol by sol-gel method to get TiO3 film with high catalytic activity. This invention provides a method for preparing TiO2 film with high light catalytic activity characterizing in reducing transformation temperature of TiO2 film and getting high catalytic degradation efficiency of methy1 orange decomposition as high as 32%-67% under visible light.
Description
Technical field
The invention belongs to photocatalyst material technology of preparing scope, particularly a kind of have titanium deoxid film of high catalytic activity and preparation method thereof under visible light.
Background technology
TiO
2Nano thin-film is a kind of important functional material, tempting application prospect is arranged, based on the TiO of sol-gel method aspect photocatalytic degradation
2Method for manufacturing thin film is to use more titanium deoxid film preparation method at present.But the TiO that utilizes such preparation method to make
2The catalyzed degradation performance need of thin-film material can show under UV-irradiation preferably, and this has brought very big difficulty to practical application.And because TiO
2Needed thermal treatment temp is than higher (more than 500 ℃) in the film preparation process, and this had both wasted a large amount of energy, had limited TiO again
2The application of film on the lower glass basis of softening temperature.At publication number CN1312337A, name is called " TiO
2Sol-gel paint and its production and application " patent application in, a kind of TiO is disclosed
2Sol-gel paint and its production and application, the main component of this colloidal sol comprise metatitanic acid fat or titanate 3%-50%, alcohol amine compound 1%-20%, water 1%-20%, the nano level TiO that forms at matrix surface through mixed colloidal sol and this colloidal sol
2Film.This invents prepared thin-film material thermal treatment temp is 450-550 ℃.
The purpose of this invention is to provide and a kind ofly under visible light, have titanium deoxid film of high catalytic activity and preparation method thereof.Technical conceive of the present invention is such:
By sol-gel method at TiO
2Add lithium salts and antimonic salt in the colloidal sol, under the low-temperature heat treatment condition, obtain to have the titanium deoxid film of high catalytic activity under visible light, the moiety of its titanium deoxid film is (weight percent):
Metatitanic acid fat 10%-30%
Alcoholic solvent 40%-60%
Stablizer 10%-30%
Water 5%-20%
Acid catalyst 1%-5%
Lithium salts 0.5-5%
Antimonic salt 0.5-3%
Described metatitanic acid fat is tetrabutyl titanate, isopropyl titanate or titanium ethanolate.
Described alcoholic solvent is ethanol, propyl alcohol or Virahol.
Described stablizer is methyl ethyl diketone or trolamine.
Described acid catalyst is hydrochloric acid, acetic acid or nitric acid.
Described lithium salts is lithium nitrate or lithium chloride.
Described antimonic salt is nitric acid antimony or antimony chloride.
The titanium deoxid film preparation method's of high catalytic activity step:
(1) according to weight percent 10%-30% titanic acid ester, 40%-60% alcoholic solvent, 10%-30% stablizer and 1%-5% acid catalyst are poured in the reacting appliance, at room temperature stirred 0.5-1 hour;
(2) weight percent 5%-20% waterside is stirred the limit and pour in the solution that step (1) makes, at room temperature stirred 1-2 hour;
(3) weight percent 0.5-5% lithium salts and 0.5-3% antimonic salt are joined in the colloidal sol that step (2) makes, continue to stir 2-4 hour;
(4) colloidal sol is joined in the device for coating, film to matrix surface;
(5) matrix after will filming is heat-treated, and thermal treatment temp is 300-400 ℃, naturally cools to room temperature, promptly makes the TiO that just has the high light catalytic activity under radiation of visible light
2Film.
The invention has the beneficial effects as follows the TiO that adopts the colloidal sol contain lithium salts and antimonic salt to prepare
2Thin-film material, the crystal conversion temperature of reduction titanium dioxide film obtains under visible light (natural light) irradiation the characteristic of tropeolin-D decomposition efficiency up to 32%～67% high catalyzed degradation efficient; A kind of TiO that can prepare highlight catalytic active under low thermal treatment temp is provided
2The method of thin-film material.
Embodiment
The invention provides and a kind ofly under visible light, have titanium deoxid film of high catalytic activity and preparation method thereof.Technical conceive of the present invention is such:
According to the semiconductor defect theory, the Sb ionic adds, and can change TiO
2Corresponding level structure, the degree of expansion and the absorption intensity that enable in visible-range are all strengthened.And by sol-gel method at TiO
2Add LiNO in the colloidal sol
3Method, can reduce TiO
2The crystal conversion temperature of film from unformed to the anatase octahedrite phase, and under the low-temperature heat treatment condition, obtain the TiO of the higher anatase octahedrite phase of density
2Film.Therefore, simultaneously Sb, Li ion are mixed TiO
2Behind the colloidal sol, can under lower thermal treatment temp, obtain the higher TiO of photocatalysis performance
2Film.
The composition of the titanium deoxid film of high catalytic activity becomes component (weight percent):
Metatitanic acid fat 10%-30%
Alcoholic solvent 40%-60%
Stablizer 10%-30%
Water 5%-20%
Acid catalyst 1%-5%
Lithium salts 0.5-5%
Antimonic salt 0.5-3%
Described metatitanic acid fat is tetrabutyl titanate, isopropyl titanate or titanium ethanolate.
Described alcoholic solvent is ethanol, propyl alcohol or Virahol.
Described stablizer is methyl ethyl diketone or trolamine.
Described acid catalyst is hydrochloric acid, acetic acid or nitric acid.
Described lithium salts is lithium nitrate or lithium chloride.
Described antimonic salt is nitric acid antimony or antimony chloride.
The titanium deoxid film preparation method's of high catalytic activity step:
(1) according to weight percent 10%-30% titanic acid ester, 40%-60% alcoholic solvent, 10%-30% stablizer and 1%-5% acid catalyst are poured in the reacting appliance, at room temperature stirred 0.5-1 hour;
(2) weight percent 5%-20% waterside is stirred the limit and pour in the solution that step (1) makes, at room temperature stirred 1-2 hour;
(3) weight percent 0.5-5% lithium salts and 0.5-3% antimonic salt are joined in the colloidal sol that step (2) makes, continue to stir 2-4 hour;
(4) colloidal sol is joined in the device for coating, film to matrix surface;
(5) matrix after will filming is heat-treated, and thermal treatment temp is 300-400 ℃, naturally cools to room temperature, promptly makes the TiO film that just has the high light catalytic activity under radiation of visible light.
Preferred TiO
2The weight percent content of colloidal sol component is:
Metatitanic acid fat 15%-20%
Alcoholic solvent 40%-50%
Stablizer 15%-20%
Water 10%-20%
Acid catalyst 1%-3%
Lithium salts 1%-3%
Antimonic salt 1%-2%
Lifting specific embodiment is below again further specified the present invention.
Embodiment 1:
(1) 54% ethanol, 15% tetrabutyl titanate, 15% methyl ethyl diketone and 1% hydrochloric acid are poured in the reacting appliance, at room temperature stirred 0.5-1 hour;
(2) 15% water is slowly poured in the solution that step (1) makes, at room temperature stirred 1-2 hour;
(3) colloidal sol is joined in the device for coating, will treat that the coated glass surface cleaning is clean, put into device for coating and film, film and generally can take crystal pulling method, rotational method etc., the glass after filming is heat-treated, thermal treatment temp is 350 ℃, naturally cool to room temperature, promptly make TiO
2Film.
Embodiment 2
(1) TiO
2The colloidal sol preparation:
Get isopropyl titanate 15%, methyl ethyl diketone 15%, propyl alcohol 50%, water 15% and hydrochloric acid 1% by weight percentage, with the step among the embodiment 1 (1), step (2) preparation;
(2) lithium nitrate 2% and antimony chloride 2% are joined in the colloidal sol that step (1) makes, continue to stir 2-4 hour;
(3) film
With embodiment 1.
Embodiment 3
Getting weight percent is that tetrabutyl titanate 15%, methyl ethyl diketone 15%, ethanol 52%, water 15%, hydrochloric acid 1% and lithium nitrate 2% are by preparing with the step among the embodiment 2.
Embodiment 4
Getting weight percent is that tetrabutyl titanate 15%, methyl ethyl diketone 15%, ethanol 52%, water 15%, hydrochloric acid 1%, nitric acid antimony 2% are by preparing with the step among the embodiment 2.
Embodiment 5
Getting weight percent is that isopropyl titanate 13%, methyl ethyl diketone 13%, Virahol 56%, water 13%, acetic acid 2% and lithium chloride 1%, antimony chloride 2% are by preparing with the step among the embodiment 2.
Embodiment 6
Getting weight percent is that titanium ethanolate 18%, trolamine 18%, propyl alcohol 40%, water 18%, nitric acid 2% and lithium chloride 2%, antimony chloride 2% are by preparing with the step among the embodiment 2.
The sample that embodiment 1,2,3,4 is obtained is numbered 1# respectively, 2#, and 3#, 4# carries out X-ray diffraction analysis and Raman spectrum analysis to film, and the result shows that the titanium dioxide film of 1# sample is mainly unformed phase; The titanium dioxide film of 2# sample is mainly the anatase octahedrite phase; The titanium dioxide film of 3# sample is mainly the anatase octahedrite phase; The titanium dioxide film of 4# sample is mainly unformed phase.More than show, add the crystal conversion temperature that lithium nitrate can reduce titanium dioxide film.
In order to check the photocatalytic degradation performance of film, the present invention selects for use tropeolin-D as the photocatalytic degradation object.Four kinds of samples are carried out the photocatalytic degradation performance test respectively, and testing tool uses HP8452A type ultra-violet and visible spectrophotometer.The 10*20mm sample is dipped in the test tube of methyl orange aqueous solution that 10ml concentration is 20mg/L, test tube is placed under the natural light irradiation 2 hours respectively, use air pump bubbling air in solution therebetween, its flow is 200ml/min, measure the tropeolin-D change in concentration, calculate decomposition efficiency, the result shows (seeing the following form 1), and the titanium dioxide film that adds lithium ion and antimony ion just can embody the high performance of catalyzed degradation efficient under visible light (natural light) irradiation.
Table 1 tropeolin-D decomposition efficiency synopsis
| Sample number into spectrum | To the tropeolin-D decomposition efficiency |
| ????1# | ????5％ |
| ????2# | ????67％ |
| ????3# | ????18％ |
| ????4# | ????32％ |
Claims (8)
1. titanium deoxid film that has high catalytic activity under visible light is characterized in that: by sol-gel method at TiO
2Add lithium salts and antimonic salt in the colloidal sol, under the low-temperature heat treatment condition, obtain to have the titanium deoxid film of high catalytic activity under visible light, the moiety of its titanium deoxid film is (weight percent):
Metatitanic acid fat 10%-30%
Alcoholic solvent 40%-60%
Stablizer 10%-30%
Water 5%-20%
Acid catalyst 1%-5%
Lithium salts 0.5-5%
Antimonic salt 0.5-3%
2. according to the described titanium deoxid film that has high catalytic activity under visible light of claim 1, it is characterized in that: described metatitanic acid fat is tetrabutyl titanate, isopropyl titanate or titanium ethanolate.
3. according to the described titanium deoxid film that has high catalytic activity under visible light of claim 1, it is characterized in that: described alcoholic solvent is ethanol, propyl alcohol or Virahol.
4. according to the described titanium deoxid film that has high catalytic activity under visible light of claim 1, it is characterized in that: described stablizer is methyl ethyl diketone or trolamine.
5. according to the described titanium deoxid film that has high catalytic activity under visible light of claim 1, it is characterized in that: described acid catalyst is hydrochloric acid, acetic acid or nitric acid.
6. according to the described titanium deoxid film that has high catalytic activity under visible light of claim 1, it is characterized in that: described lithium salts is lithium nitrate, lithium chloride.
7. according to the described titanium deoxid film that has high catalytic activity under visible light of claim 1, it is characterized in that: described antimonic salt is nitric acid antimony, antimony chloride.
8. titanium deoxid film preparation method who under visible light, has high catalytic activity, it is characterized in that: the titanium deoxid film preparation method's of described high catalytic activity step is:
(1) according to weight percent 10%-30% titanic acid ester, 40%-60% alcoholic solvent, 10%-30% stablizer and 1%-5% acid catalyst are poured in the reacting appliance, at room temperature stirred 0.5-1 hour;
(2) the 5%-20% waterside is stirred the limit and pour in the solution that step (1) makes, at room temperature stirred 1-2 hour;
(3) 0.5-5% lithium salts and 0.5-3% antimonic salt are joined in the colloidal sol that step (2) makes, continue to stir 2-4 hour;
(4) colloidal sol is joined in the device for coating, film to matrix surface;
(5) matrix after will filming is heat-treated, and thermal treatment temp is 300-400 ℃, naturally cools to room temperature, promptly makes the TiO that just has the high light catalytic activity under radiation of visible light
2Film.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200410033800 CN1269992C (en) | 2004-04-20 | 2004-04-20 | Titania thin film possessing high catalytic activity under visible light and preparation method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200410033800 CN1269992C (en) | 2004-04-20 | 2004-04-20 | Titania thin film possessing high catalytic activity under visible light and preparation method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1563490A true CN1563490A (en) | 2005-01-12 |
| CN1269992C CN1269992C (en) | 2006-08-16 |
Family
ID=34481403
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 200410033800 Expired - Fee Related CN1269992C (en) | 2004-04-20 | 2004-04-20 | Titania thin film possessing high catalytic activity under visible light and preparation method |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1269992C (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101037553B (en) * | 2007-02-13 | 2010-04-21 | 云南大学 | Preparation and application method of optically catalysed environment protection type coating |
| CN102580708A (en) * | 2012-01-06 | 2012-07-18 | 上海交通大学 | Method for preparing nitrogen modified titanium dioxide sol with visible-light catalytic activity |
| CN102888598A (en) * | 2012-10-12 | 2013-01-23 | 浙江大学 | Preparation method of titanium dioxide based selective absorbing thin film |
| CN109603805A (en) * | 2018-12-28 | 2019-04-12 | 上海纳米技术及应用国家工程研究中心有限公司 | Preparation method of antimony bismuthic acid zinc self-assembled nanometer stick of self supporting structure and products thereof and application |
| CN116870887A (en) * | 2023-06-26 | 2023-10-13 | 厦门大学 | Titanium dioxide carrier-loaded metal nano catalyst and application thereof |
-
2004
- 2004-04-20 CN CN 200410033800 patent/CN1269992C/en not_active Expired - Fee Related
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101037553B (en) * | 2007-02-13 | 2010-04-21 | 云南大学 | Preparation and application method of optically catalysed environment protection type coating |
| CN102580708A (en) * | 2012-01-06 | 2012-07-18 | 上海交通大学 | Method for preparing nitrogen modified titanium dioxide sol with visible-light catalytic activity |
| 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 |
| CN102888598A (en) * | 2012-10-12 | 2013-01-23 | 浙江大学 | Preparation method of titanium dioxide based selective absorbing thin film |
| CN109603805A (en) * | 2018-12-28 | 2019-04-12 | 上海纳米技术及应用国家工程研究中心有限公司 | Preparation method of antimony bismuthic acid zinc self-assembled nanometer stick of self supporting structure and products thereof and application |
| CN109603805B (en) * | 2018-12-28 | 2021-07-20 | 上海纳米技术及应用国家工程研究中心有限公司 | Preparation method of self-supporting zinc antimonate self-assembled nanorod, product and application thereof |
| CN116870887A (en) * | 2023-06-26 | 2023-10-13 | 厦门大学 | Titanium dioxide carrier-loaded metal nano catalyst and application thereof |
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| Publication number | Publication date |
|---|---|
| CN1269992C (en) | 2006-08-16 |
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