CN1962511A - Process for preparing porous TiO2 film with high photocatalytic activity - Google Patents
Process for preparing porous TiO2 film with high photocatalytic activity Download PDFInfo
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- CN1962511A CN1962511A CNA2006101549488A CN200610154948A CN1962511A CN 1962511 A CN1962511 A CN 1962511A CN A2006101549488 A CNA2006101549488 A CN A2006101549488A CN 200610154948 A CN200610154948 A CN 200610154948A CN 1962511 A CN1962511 A CN 1962511A
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- 230000001699 photocatalysis Effects 0.000 title claims abstract description 10
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title abstract description 17
- 238000004519 manufacturing process Methods 0.000 title abstract description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 16
- 238000006243 chemical reaction Methods 0.000 claims abstract description 14
- 239000000758 substrate Substances 0.000 claims abstract description 14
- 238000002360 preparation method Methods 0.000 claims abstract description 13
- 229910010413 TiO 2 Inorganic materials 0.000 claims abstract description 12
- 239000011521 glass Substances 0.000 claims abstract description 10
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 10
- 239000007789 gas Substances 0.000 claims abstract description 9
- 239000012159 carrier gas Substances 0.000 claims abstract description 5
- 238000004140 cleaning Methods 0.000 claims abstract description 5
- 229910052734 helium Inorganic materials 0.000 claims abstract description 5
- 239000001307 helium Substances 0.000 claims abstract description 3
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims abstract description 3
- 230000003197 catalytic effect Effects 0.000 claims description 6
- 238000000151 deposition Methods 0.000 claims description 6
- 238000005530 etching Methods 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 4
- 239000000376 reactant Substances 0.000 claims description 4
- 238000005268 plasma chemical vapour deposition Methods 0.000 claims description 2
- 239000010408 film Substances 0.000 abstract description 28
- 238000000034 method Methods 0.000 abstract description 6
- 238000005229 chemical vapour deposition Methods 0.000 abstract description 5
- 239000010409 thin film Substances 0.000 abstract description 5
- 125000002887 hydroxy group Chemical group [H]O* 0.000 abstract description 2
- 238000000623 plasma-assisted chemical vapour deposition Methods 0.000 abstract description 2
- 239000010453 quartz Substances 0.000 abstract description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 abstract description 2
- 230000015572 biosynthetic process Effects 0.000 abstract 1
- 239000012495 reaction gas Substances 0.000 abstract 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 10
- 238000003980 solgel method Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 230000000536 complexating effect Effects 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000007146 photocatalysis Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 230000001954 sterilising effect Effects 0.000 description 1
- 238000004659 sterilization and disinfection Methods 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
- C03C17/22—Surface treatment of glass, not in the form of fibres or filaments, by coating with other inorganic material
- C03C17/23—Oxides
- C03C17/245—Oxides by deposition from the vapour phase
- C03C17/2456—Coating containing TiO2
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C15/00—Surface treatment of glass, not in the form of fibres or filaments, by etching
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
- C03C17/006—Surface treatment of glass, not in the form of fibres or filaments, by coating with materials of composite character
- C03C17/007—Surface treatment of glass, not in the form of fibres or filaments, by coating with materials of composite character containing a dispersed phase, e.g. particles, fibres or flakes, in a continuous phase
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C2217/00—Coatings on glass
- C03C2217/20—Materials for coating a single layer on glass
- C03C2217/21—Oxides
- C03C2217/212—TiO2
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C2217/00—Coatings on glass
- C03C2217/40—Coatings comprising at least one inhomogeneous layer
- C03C2217/425—Coatings comprising at least one inhomogeneous layer consisting of a porous layer
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C2217/00—Coatings on glass
- C03C2217/40—Coatings comprising at least one inhomogeneous layer
- C03C2217/43—Coatings comprising at least one inhomogeneous layer consisting of a dispersed phase in a continuous phase
- C03C2217/46—Coatings comprising at least one inhomogeneous layer consisting of a dispersed phase in a continuous phase characterized by the dispersed phase
- C03C2217/47—Coatings comprising at least one inhomogeneous layer consisting of a dispersed phase in a continuous phase characterized by the dispersed phase consisting of a specific material
- C03C2217/475—Inorganic materials
- C03C2217/477—Titanium oxide
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C2218/00—Methods for coating glass
- C03C2218/10—Deposition methods
- C03C2218/15—Deposition methods from the vapour phase
- C03C2218/152—Deposition methods from the vapour phase by cvd
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- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Geochemistry & Mineralogy (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Dispersion Chemistry (AREA)
- Composite Materials (AREA)
- Catalysts (AREA)
Abstract
本发明公开的具有高光催化活性的多孔TiO2薄膜的制备方法，步骤如下：将玻璃基板清洗后，置于石英平板上，一起放入等离子体化学气相沉积装置反应室的上下电极板之间；先向反应室通入氦气和氮气的混合气体，用产生的等离子体对加热至400～500℃的玻璃基板进行刻蚀处理；再通入以氮气为载气的TiCl4反应气体，流量为0.10－0.15m3/h，利用常压等离子体增强化学气相沉积法制备TiO2薄膜。本发明方法制得的TiO2薄膜为多孔状，其比表面积大、表面羟基含量高，光催化活性比通常CVD制备的TiO2薄膜可提高1倍左右；可以实现大面积快速制备多孔TiO2薄膜，且成膜均匀、工艺稳定、适合于工业化规模生产。The preparation method of the porous TiO2 thin film with high photocatalytic activity disclosed by the present invention has the following steps: after cleaning the glass substrate, place it on a quartz plate, and put it together between the upper and lower electrode plates in the reaction chamber of a plasma chemical vapor deposition device; The mixed gas of helium and nitrogen is first introduced into the reaction chamber, and the glass substrate heated to 400-500 °C is etched with the generated plasma; then TiCl 4 reaction gas with nitrogen as the carrier gas is introduced, and the flow rate is 0.10-0.15m 3 /h, using atmospheric pressure plasma enhanced chemical vapor deposition method to prepare TiO 2 film. The TiO2 thin film prepared by the method of the present invention is porous, has a large specific surface area and high surface hydroxyl content, and its photocatalytic activity can be improved by about 1 time compared with the TiO2 thin film prepared by conventional CVD; it can realize rapid preparation of porous TiO2 thin film in a large area , and the film formation is uniform, the process is stable, and it is suitable for industrial scale production.
Description
Technical field
The present invention relates to TiO
2The preparation method of film especially has high-optical catalytic porous TiO
2The preparation method of film.
Background technology
Titanium dioxide (TiO
2) photocatalytic activity mainly determined to have the film attitude TiO of photocatalytic activity by its anatase octahedrite phase content and surface light catalytic Contact area
2Has application potential widely.
Preparation TiO
2The method of film has a lot, as: CN02119304.5 adopts the mesoporous TiO of the complexing Prepared by Sol Gel Method high photolytic activity of a kind of high sterilization
2Film; CN200510019713.3 adopts the salts solution high temperature pyrolytic cracking (HTP) to prepare c axle preferrel orientation TiO
2Film; CN01141981.4 addresses the nano-TiO of high-specific surface area
2The preparation method of film; CN03818226.2 adopts Atomospheric pressure glow discharge plasma assisted CVD low temperature to prepare TiO
2Film, etc.Wherein, have the feasibility of suitability for industrialized production most with CVD deposition techniques large-area titanium dioxide thin film, still, the photochemical catalysis TiO of CVD technology preparation
2Film has smooth even curface, and its anatase octahedrite phase content is low than the film of Prepared by Sol Gel Method, and therefore, photocatalysis performance reaches optimum level far away.
Summary of the invention
The purpose of this invention is to provide a kind of high-optical catalytic porous TiO that has
2The preparation method of film.
Of the present invention have a high-optical catalytic porous TiO
2The preparation method of film, its step is as follows:
1) with after the glass substrate cleaning, places on the quartzy flat board, put into together between the upper and lower battery lead plate of plasma CVD device reaction chamber;
2) to the mixed gas of reaction chamber feeding helium and nitrogen, throughput ratio is He: N
2=2～5: 5, the air pressure of control reaction chamber is a normal atmosphere, opens the plasma exciatiaon pulse power, and voltage of supply is 1～5kV, 10～20 minutes post-heating substrate temperature to 400～500 ℃ utilize the plasma body that produces that glass substrate is carried out etching processing;
3) feeding with nitrogen is the TiCl of carrier gas
4Reactant gases, flow are 0.10-0.15m
3/ h, adjusting plasma exciatiaon pulse power voltage is 10～20kV, depositing Ti O
2Film.
Step 1) of the present invention is placed quartz plate between the power-on and power-off pole plate, be in order to realize plasma discharge under the normal atmosphere, usually, make quartzy dull and stereotyped thickness below 2mm that plasma discharge is affected under the normal atmosphere not make.
Beneficial effect of the present invention is:
1. the present invention adopts plasma discharge depositing Ti O under atmospheric pressure
2Film, prepared TiO
2Film is a vesicular, and its specific surface area is big, The adsorbed hydroxyl content is high, and photocatalytic activity is than the TiO of common CVD preparation
2Film can improve about 1 times.
2. the inventive method can realize that big area prepares porous TiO fast
2Film, and film forming evenly, process stabilizing, be suitable for commercial scale production.
Description of drawings
Fig. 1 is porous TiO
2The scanning electron photomicrograph of film.
Embodiment
Further specify the present invention below in conjunction with embodiment.
Embodiment 1
1) with after the glass substrate cleaning, place on the quartzy flat board of 2mm, put into together between the upper and lower battery lead plate of atmospheric pressure plasma chemical vapor deposition unit reaction chamber;
2) feed He and N to reaction chamber
2Mixed gas, throughput ratio is He: N
2=2: 5, control reaction chamber air pressure is a normal atmosphere, opens the plasma exciatiaon pulse power, supply frequency 1.2kHz, voltage 5kV, and 10 minutes post-heating substrate temperatures to 400 ℃ utilize the plasma body that produces that glass substrate is carried out etching processing;
3) feeding with nitrogen is the TiCl of carrier gas
4Reactant gases, flow are 0.15m
3/ h, adjusting plasma exciatiaon pulse power voltage is 10kV, depositing Ti O
2Film.
Prepared TiO
2Film has the microstructure features (see figure 1) of vertical orientated growth and porous surface, and its empty size is at 200～300nm.The TiO that photocatalytic activity makes than common CVD method
2Film doubles.
Embodiment 2
1) with after the glass substrate cleaning, place on the quartzy flat board of 1.8mm, put into together between the upper and lower battery lead plate of atmospheric pressure plasma chemical vapor deposition unit reaction chamber;
2) feed He and N to reaction chamber
2Mixed gas, throughput ratio is He: N
2=1: 1, control reaction chamber air pressure is a normal atmosphere, opens the plasma exciatiaon pulse power, supply frequency 1.2kHz, voltage 1kV, and 20 minutes post-heating substrate temperatures to 500 ℃ utilize the plasma body that produces that glass substrate is carried out etching processing;
3) feeding with nitrogen is the TiCl of carrier gas
4Reactant gases, flow are 0.10m
3/ h, adjusting plasma exciatiaon pulse power voltage is 20kV, depositing Ti O
2Film.
Prepared TiO
2Film have equally as shown in Figure 1 vertical orientated growth and the microstructure features of porous surface, its empty size is at 200～300nm.The TiO that photocatalytic activity makes than common CVD method
2Film doubles.
Claims (2)
1. has high-optical catalytic porous TiO
2The preparation method of film is characterized in that step is as follows:
1) with after the glass substrate cleaning, places on the quartzy flat board, put into together between the upper and lower battery lead plate of plasma CVD device reaction chamber;
2) to the mixed gas of reaction chamber feeding helium and nitrogen, throughput ratio is He: N
2=2～5: 5, the air pressure of control reaction chamber is a normal atmosphere, opens the plasma exciatiaon pulse power, and voltage is 1～5kV, and 10～20 minutes post-heating substrate temperature to 400～500 ℃ utilize the plasma body that produces that glass substrate is carried out etching processing;
3) feeding with nitrogen is the TiCl of carrier gas
4Reactant gases, flow are 0.10-0.15m
3/ h, adjusting plasma exciatiaon pulse power voltage is 10～20kV, depositing Ti O
2Film.
2. the porous TiO with photocatalytic activity according to claim 1
2The preparation method of film is characterized in that said quartzy slab-thickness is below 2mm in the step 1).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2006101549488A CN1962511A (en) | 2006-11-30 | 2006-11-30 | Process for preparing porous TiO2 film with high photocatalytic activity |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2006101549488A CN1962511A (en) | 2006-11-30 | 2006-11-30 | Process for preparing porous TiO2 film with high photocatalytic activity |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1962511A true CN1962511A (en) | 2007-05-16 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNA2006101549488A Pending CN1962511A (en) | 2006-11-30 | 2006-11-30 | Process for preparing porous TiO2 film with high photocatalytic activity |
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| CN (1) | CN1962511A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2287120A1 (en) * | 2009-07-16 | 2011-02-23 | AGC Glass Europe | Decorative glass article |
| CN105648425A (en) * | 2014-11-20 | 2016-06-08 | 理想能源设备(上海)有限公司 | Chemical vapor deposition device and temperature control method thereof |
| CN107576678A (en) * | 2017-09-06 | 2018-01-12 | 四川龙蟒钛业股份有限公司 | A kind of evaluation method of calcining seeds activity |
| CN110028252A (en) * | 2019-05-22 | 2019-07-19 | 西安工业大学 | A method of improving substrate of glass heating coating job stability |
-
2006
- 2006-11-30 CN CNA2006101549488A patent/CN1962511A/en active Pending
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2287120A1 (en) * | 2009-07-16 | 2011-02-23 | AGC Glass Europe | Decorative glass article |
| WO2011006883A3 (en) * | 2009-07-16 | 2011-06-23 | Agc Glass Europe | Decorative glass article |
| CN105648425A (en) * | 2014-11-20 | 2016-06-08 | 理想能源设备(上海)有限公司 | Chemical vapor deposition device and temperature control method thereof |
| CN105648425B (en) * | 2014-11-20 | 2018-06-26 | 理想能源设备(上海)有限公司 | A kind of chemical vapor deposition unit and its temperature control method |
| CN107576678A (en) * | 2017-09-06 | 2018-01-12 | 四川龙蟒钛业股份有限公司 | A kind of evaluation method of calcining seeds activity |
| CN107576678B (en) * | 2017-09-06 | 2020-10-20 | 龙佰四川钛业有限公司 | Method for evaluating activity of calcined seed crystal |
| CN110028252A (en) * | 2019-05-22 | 2019-07-19 | 西安工业大学 | A method of improving substrate of glass heating coating job stability |
| CN110028252B (en) * | 2019-05-22 | 2020-09-11 | 西安工业大学 | A method for improving the working stability of a heating coating on a glass substrate |
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Open date: 20070516 |