CN101205119A - Method for preparing titanium dioxide film with phase separation structure - Google Patents
Method for preparing titanium dioxide film with phase separation structure Download PDFInfo
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- CN101205119A CN101205119A CNA2006101695573A CN200610169557A CN101205119A CN 101205119 A CN101205119 A CN 101205119A CN A2006101695573 A CNA2006101695573 A CN A2006101695573A CN 200610169557 A CN200610169557 A CN 200610169557A CN 101205119 A CN101205119 A CN 101205119A
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- separation structure
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- titanium deoxid
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Abstract
The invention relates to a method for preparing titanium dioxide film with phase separation structure, which is the method for inducing the phase separation by using photopolymerization. The method includes the process: a polymer monomer with easy polymerization is added in sol of a coating; the prepared film after impregnation and lifting is irradiated by ultraviolet light to induce the reaction of monomer polymerization, which leads to the formation of the phase structure on the surface of the film; at last, the titanium dioxide film with anatase style is prepared through a thermal treatment.By adopting the invention, an anatase crystal-style titanium dioxide film with a two-dimensional spindal phase separation structure and a porous structure can be obtained. Grain boundary of grain does not exist in the film and the film presents upstanding photocatalysis performance.The preparing method in the invention avoids the existing defects in the prior method and can simply realize the regulation and control of surface appearance of the film and sizes of micro regions through changing reaction conditions such as the types of monomers, light application time, types of light sources etc.The invention has the simple process, strong controllability and high repetition rate of the film structure.
Description
Technical field
The invention belongs to technical field of function materials, specifically relate to a kind of preparation method with titanium deoxid film of phase separation structure.
Background technology
1972, professor Fujishima of Japan found the photocatalysis performance of titanium dioxide first, has begun new era of heterogeneous photoelectrocatalysis.Since then, this field has caused scientific worker's very big concern.1991, with M. of engineering institute such as Lausanne, SUI height
Research group headed by the professor adopts the nanoporous TiO of high-specific surface area
2Film is made semi-conducting electrode, make dyestuff with organic compound such as transition metal Ru and Os, and select for use suitable redox electrolytes matter to develop a kind of nano-crystalline photoelectric chemistry solar cell, the development that appears as photoelectrochemical cell of this battery has brought revolutionary innovation.For the photocatalysis performance that improves titanium dioxide and the photoelectric transformation efficiency of dye sensitization solar battery, usually need preparation to have high specific surface area porous titanium dioxide thin-film, can make film have more active centre like this, can also guarantee the monolayer adsorption of dyestuff on the other hand at film surface.This is that the existence of multilayer sensitizing agent can hinder the conveying of electronics on the contrary, causes the photovoltaic energy conversion rate to descend because having only the sensitizing agent molecule of very close titanium dioxide surface to be injected into the electronics of excited state smoothly in the titanium dioxide conduction band goes.
The preparation method of this nanocrystalline porous titanium dioxide of preparation mainly contains powder coated method (as Japanese kokai publication hei 10-212120 communique) and sol-gel method (as Japanese kokai publication hei 11-310898 communique) at present.Adopt the titanium deoxid film and the substrate contacts area of the preparation of powder coated method little, in conjunction with firm inadequately, film is easy to split away off from substrate between the two.Adopt that the sol-gel method synthesis temperature is low, product purity is high, good uniformity, chemical ingredients is accurate, film forming is even, technology is simple, remains preparation nanoporous TiO
2The method that film is the most frequently used.People such as Kajihara are at document 1:Journal of American Ceramic.Society, and 1998, among the 81:2670-2676, reported that the employing polyoxyethylene glycol prepares porous TiO
2The method of film, this has become preparation porous TiO
2A kind of method that film is very conventional, many subsequently investigators have done a large amount of fruitful researchs to this system again.But this method also has the shortcoming that itself is difficult to overcome: film be separated and itself gelation takes place simultaneously, general being difficult to controlled it, and the final surface topography of film often is subjected to the influence of environment such as many factors such as speed of the humidity of air and coating operation process such as plated film, thereby the repeatability of film morphology is not high.
Summary of the invention
The objective of the invention is to overcome all deficiency of prior art when the preparation titanium deoxid film, thereby provide a kind of high preparation of membrane structure repeatability with low cost, easy and simple to handle, that obtain to have the method for the titanium deoxid film of phase separation structure.
Goal of the invention of the present invention realizes by the following technical solutions:
Preparation method with titanium deoxid film of phase separation structure provided by the invention, it is for utilizing the isolating method of photopolymerization induction phase, in the colloidal sol of plated film, add and be easy to the polymeric high polymer monomer, the film that dipping is lifted back preparation carries out ultraviolet lighting and comes the initiation reaction monomer polymerization, cause the formation of film surface phase separation structure, prepare the anatase titanium dioxide film by thermal treatment at last, specifically comprise following step:
1) quartz base plate is used washing composition, distilled water, ethanol, acetone wash clean respectively, and 600 ℃ of following thermal treatments 10 minutes;
2) with isopropyl titanate in 0 ℃ of mixing solutions that is dissolved in ethanol and dimethyl formamide, stirring 10min makes it to mix, slowly splash into water and nitric acid, the mol ratio of isopropyl titanate, dimethyl formamide, water, ethanol, each reactant of nitric acid is 1: 4: 1.5～3.5: 8: 0.3～0.7 in the solution; Mix the azo-bis-isobutyl cyanide of back adding routine dose, be stirred to dissolving;
Described routine dose is meant according to high polymer monomer quality 1% and adds azo-bis-isobutyl cyanide;
3) high polymer monomer of 0.0025mol～0.0125mol being dissolved in mass percent is in 5～7% the polyvinylpyrrolidone ethanolic soln, and with step 2) solution that obtains mixes and stirs 30min;
Described high polymer monomer is acrylamide, Dipentaerythritol hydroxyl five acrylate, tetramethylol methane tetraacrylate, pentaerythritol triacrylate and new pentane diacid diacrylate fat, TMPTA or 1,6 hexanediol diacrylate;
4) colloidal sol that step 3) is obtained adopts mode uniform film of preparation one layer thickness on the substrate that step 1) is handled of dipping plated film;
5) film that step 4) is obtained shines 10～30min under UV-light;
Described ultraviolet light wavelength is 200～400 nanometers, and power is below 500W; Can select for use low pressure mercury lamp that wavelength is 253nm at the high voltage mercury lamp of 365nm or main wavelength to realize monomer polymerization in the system of bringing out;
6) film that step 5) is obtained difference thermal treatment 10min under 200 ℃ and 600 ℃ to remove the organism in the film, obtains having the titanium deoxid film of phase separation structure.
Adopt method of the present invention, can obtain the titanium deoxid film of the anatase crystal that revolves joint phase separation structure and vesicular structure of two dimension, there is not the particulate crystal boundary in this film, and has presented extraordinary photocatalysis performance.
The present invention adds the high polymer monomer with photopolymerization performance at the colloidal sol that is used for plated film, carries out ultraviolet lighting by the film that dipping is lifted the back preparation.Because ultraviolet lighting has caused the reaction monomers polymerization, along with the further in-depth of reaction, the molecular weight of newly-generated polymkeric substance increases gradually, and this newly-generated polymkeric substance can be from monomer and the TiO of remnants
2Oligopolymer in separate.Like this at TiO
2Realized being separated between the monomer of oligopolymer-remnants and the newly-generated polymer phase.Finally organism is removed, in film, just obtained the interconnective TiO that joint is separated that revolves by thermal treatment
2Skeleton structure.
Method with respect to the existing preparation titanium deoxid film, preparation method of the present invention has avoided the shortcoming that exists in the previous methods, it is also advantageous in that: the present invention can very simply realize the surface topography and the site size of film are regulated and control by changing reaction conditionss such as monomeric species, light application time, light source kind.Present method technical process is simple, controllability strong, membrane structure repeatability height.
Description of drawings
Fig. 1 a is the optical microscope photograph (amplifying 100 times) of the titanium deoxid film of embodiment 1 preparation;
Fig. 1 b is the electron scanning micrograph (amplifying 6000 times) of the titanium deoxid film of embodiment 2 preparations;
The comparison diagram of Fig. 2 for adopting the prepared porous titanium dioxide thin-film that is separated titanium deoxid film and adopts polyoxyethylene glycol to prepare of the present invention methylene blue solution to be carried out the photodegradation reaction; Wherein, 1 for adopting the titanium deoxid film of the present invention's preparation, and 1 ' adopts the porous titanium dioxide thin-film of polyoxyethylene glycol preparation.
Embodiment
Embodiment 1,
With the quartz base plate wash clean,, cool off standby 600 ℃ of following thermal treatments 10 minutes.Under 0 ℃, be dissolved in isopropyl titanate in the mixing solutions of ethanol and dimethyl formamide, stirring 10min makes it to mix, slowly splash into water and nitric acid, the mol ratio of isopropyl titanate, dimethyl formamide, water, ethanol, each reactant of nitric acid is 1.0: 4.0: 3.0 in the solution: 8.0: 0.5.Mix the back and add the 0.05g azo-bis-isobutyl cyanide, be stirred to dissolving.Subsequently the acrylamide of 0.01mol is dissolved in mass percent and is in 5% the polyvinylpyrrolidone ethanolic soln and mix and stir 30min with solution that the front obtains.Adopt the mode of dipping plated film on ready substrate, to prepare the uniform film of a layer thickness.The film that obtains is shone 30min under low pressure mercury lamp.At last with the film after the illumination under 200 ℃ and 600 ℃ respectively thermal treatment 10min to remove the organism in the film, obtain having revolve the joint phase separation structure and the titanium deoxid film of anatase crystal.The optical microscope photograph of this film shown in Fig. 1 (a), as can be seen from the figure this film has shown a kind of joint phase separation structure that typically revolves, its site size is about 7 μ m.
Embodiment 2
With the quartz base plate wash clean,, cool off standby 600 ℃ of following thermal treatments 10 minutes.Under 0 ℃, be dissolved in isopropyl titanate in the mixing solutions of ethanol and dimethyl formamide, stirring 10min makes it to mix, slowly splash into water and nitric acid, the mol ratio of isopropyl titanate, dimethyl formamide, water, ethanol, each reactant of nitric acid is 1.0: 4.0: 1.5 in the solution: 8.0: 0.5.Mix the back and add the 0.05g azo-bis-isobutyl cyanide, be stirred to dissolving.Subsequently Dipentaerythritol hydroxyl five acrylate of 0.0025mol are dissolved in mass percent and are in 6% the polyvinylpyrrolidone ethanolic soln and mix and stir 10min with solution that the front obtains.Adopt the mode of dipping plated film on ready substrate, to prepare the uniform film of a layer thickness.The film that obtains is shone 30min under high voltage mercury lamp.At last with the film after the illumination under 200 ℃ and 600 ℃ respectively thermal treatment 10min obtain having the titanium deoxid film of the anatase crystal of vesicular structure to remove the organism in the film.As can be seen from the figure there is a large amount of empty structures in the electron scanning micrograph of this film shown in Fig. 1 (b) in this film, its average pore size is about 1 μ m.This film is carried out the methylene blue photocatalytic degradation tests this film and has shown than dense film degradation speed faster.
Embodiment 3
With the quartz base plate wash clean,, cool off standby 600 ℃ of following thermal treatments 10 minutes.Under 0 ℃, be dissolved in isopropyl titanate in the mixing solutions of ethanol and dimethyl formamide, stirring 10min makes it to mix, slowly splash into water and nitric acid, the mol ratio of isopropyl titanate, dimethyl formamide, water, ethanol, each reactant of nitric acid is 1.0: 4.0: 3.0 in the solution: 8.0: 0.7.Mix the back and add the 0.05g azo-bis-isobutyl cyanide, be stirred to dissolving.Subsequently the tetramethylol methane tetraacrylate of 0.0125mol is dissolved in mass percent and is in 7% the polyvinylpyrrolidone ethanolic soln and mix and stir 10min with solution that the front obtains.Adopt the mode of dipping plated film on ready substrate, to prepare the uniform film of a layer thickness.The film that obtains is shone 20min under high voltage mercury lamp.At last with the film after the illumination under 200 ℃ and 600 ℃ respectively thermal treatment 10min obtain having the titanium deoxid film of the anatase crystal of vesicular structure to remove the organism in the film.
Embodiment 4
With the quartz base plate wash clean,, cool off standby 600 ℃ of following thermal treatments 10 minutes.Under 0 ℃, be dissolved in isopropyl titanate in the mixing solutions of ethanol and dimethyl formamide, stirring 10min makes it to mix, slowly splash into water and nitric acid, the mol ratio of isopropyl titanate, dimethyl formamide, water, ethanol, each reactant of nitric acid is 1.0: 4.0: 3.5 in the solution: 8.0: 0.3.Mix the back and add the 0.05g azo-bis-isobutyl cyanide, be stirred to dissolving.Subsequently the pentaerythritol triacrylate of 0.01mol is dissolved in mass percent and is in 5% the polyvinylpyrrolidone ethanolic soln and mix and stir 30min with solution that the front obtains.Adopt the mode of dipping plated film on ready substrate, to prepare the uniform film of a layer thickness.The film that obtains is shone 20min under high voltage mercury lamp.At last with the film after the illumination under 200 ℃ and 600 ℃ respectively thermal treatment 10min obtain having the titanium deoxid film that revolves the anatase crystal that is separated of joint to remove the organism in the film.
Embodiment 5
With the quartz base plate wash clean,, cool off standby 600 ℃ of following thermal treatments 10 minutes.Under 0 ℃, be dissolved in isopropyl titanate in the mixing solutions of ethanol and dimethyl formamide, stirring 10min makes it to mix, slowly splash into water and nitric acid, the mol ratio of isopropyl titanate, dimethyl formamide, water, ethanol, each reactant of nitric acid is 1.0: 4.0: 3.0 in the solution: 8.0: 0.5.Mix the back and add the 0.05g azo-bis-isobutyl cyanide, be stirred to dissolving.Subsequently the new pentane diacid diacrylate fat of 0.01mol is dissolved in mass percent and is in 6% the polyvinylpyrrolidone ethanolic soln and mix and stir 30min with solution that the front obtains.Adopt the mode of dipping plated film on ready substrate, to prepare the uniform film of a layer thickness.The film that obtains is shone 30min under high voltage mercury lamp.At last with the film after the illumination under 200 ℃ and 600 ℃ respectively thermal treatment 10min obtain having the titanium deoxid film of the anatase crystal of vesicular structure to remove the organism in the film.
Embodiment 6
With the quartz base plate wash clean,, cool off standby 600 ℃ of following thermal treatments 10 minutes.Under 0 ℃, be dissolved in isopropyl titanate in the mixing solutions of ethanol and dimethyl formamide, stirring 10min makes it to mix, slowly splash into water and nitric acid, the mol ratio of isopropyl titanate, dimethyl formamide, water, ethanol, each reactant of nitric acid is 1.0: 4.0: 3.0 in the solution: 8.0: 0.5.Mix the back and add the 0.05g azo-bis-isobutyl cyanide, be stirred to dissolving.Subsequently the TMPTA of 0.075mol is dissolved in mass percent and is in 6% the polyvinylpyrrolidone ethanolic soln and mix and stir 30min with solution that the front obtains.Adopt the mode of dipping plated film on ready substrate, to prepare the uniform film of a layer thickness.The film that obtains is shone 20min under high voltage mercury lamp.At last with the film after the illumination under 200 ℃ and 600 ℃ respectively thermal treatment 10min obtain having the titanium deoxid film of the anatase crystal of vesicular structure to remove the organism in the film.
Embodiment 7
With the quartz base plate wash clean,, cool off standby 600 ℃ of following thermal treatments 10 minutes.Under 0 ℃, be dissolved in isopropyl titanate in the mixing solutions of ethanol and dimethyl formamide, stirring 10min makes it to mix, slowly splash into water and nitric acid, the mol ratio of isopropyl titanate, dimethyl formamide, water, ethanol, each reactant of nitric acid is 1.0: 4.0: 2.5 in the solution: 8.0: 0.5.Mix the back and add the 0.05g azo-bis-isobutyl cyanide, be stirred to dissolving.Subsequently the 1,6 hexanediol diacrylate of 0.0125mol is dissolved in mass percent and is in 5% the polyvinylpyrrolidone ethanolic soln and mix and stir 30min with solution that the front obtains.Adopt the mode of dipping plated film on ready substrate, to prepare the uniform film of a layer thickness.The film that obtains is shone 30min under high voltage mercury lamp.At last with the film after the illumination under 200 ℃ and 600 ℃ respectively thermal treatment 10min obtain having the titanium deoxid film of the anatase crystal of vesicular structure to remove the organism in the film.
Embodiment 8
Employing Dipentaerythritol hydroxyl five the acrylate film for preparing and the porous titanium dioxide thin-film that adopts the polyoxyethylene glycol preparation that method prepares in the document 1 of embodiment 2 preparations are carried out methylene blue photocatalytic degradation contrast experiment.Configuration concentration is 6 * 10
-5The aqueous solution of methylene blue of M is got 2.5ml and is injected one except that top and bottom, in the quartz container of other four faces without any frosted processing.Respectively with the titanium deoxid film of embodiment 2 preparation with adopt the porous titanium dioxide thin-film of method preparation in the document 1 to cut out to be the thin slice (one side of handling without frosted with quartz container is identical or smaller) of 6 * 15mm, to keep flat in the quartz container that lid covers and seals to area.Being placed on this quartz container apart from intensity is 150mW/cm
2Xe lamp 50cm place carry out illumination.Adopted ultraviolet-visible absorption spectroscopy that the absorption of methylene blue is measured in per 10 minutes.Methylene blue solution is carried out in the photodegradation reaction relatively as can be seen as shown in Figure 2, it is more that the concentration of methylene blue that the porous titanium dioxide thin-film (curve 2) that the titanium deoxid film (curve 1) that adopts the present invention to prepare prepares than the employing polyoxyethylene glycol can make in the identical time reduces, i.e. the film of the present invention preparation shows better photocatalysis performance.
Claims (7)
1. preparation method with titanium deoxid film of phase separation structure comprises following step:
1) with the quartz base plate wash clean, and 600 ℃ of following thermal treatments;
2) with isopropyl titanate in 0 ℃ of mixing solutions that is dissolved in ethanol and dimethyl formamide, stirring makes it to mix, slowly splash into water and nitric acid, the mol ratio of isopropyl titanate, dimethyl formamide, water, ethanol, each reactant of nitric acid is 1: 4: 1.5～3.5: 8: 0.3～0.7 in the solution; Mix the azo-bis-isobutyl cyanide of back adding routine dose, be stirred to dissolving;
3) high polymer monomer of 0.0025mol～0.0125mol being dissolved in is in the polyvinylpyrrolidone ethanolic soln of 5～7wt%, and with step 2) solution that obtains mixes stirring;
Described high polymer monomer is acrylamide, Dipentaerythritol hydroxyl five acrylate, tetramethylol methane tetraacrylate, pentaerythritol triacrylate and new pentane diacid diacrylate fat, TMPTA or 1,6 hexanediol diacrylate;
4) colloidal sol that step 3) is obtained adopts mode uniform film of preparation one layer thickness on the substrate that step 1) is handled of dipping plated film;
5) film that step 4) is obtained shines 10～30min under UV-light;
6) film that step 5) is obtained obtains having the titanium deoxid film of phase separation structure 200 ℃ and 600 ℃ of thermal treatments respectively down.
2. the preparation method with titanium deoxid film of phase separation structure as claimed in claim 1 is characterized in that: use washing composition, distilled water, ethanol, acetone with the quartz base plate wash clean in the described step 1) respectively.
3. the preparation method with titanium deoxid film of phase separation structure as claimed in claim 1 is characterized in that: heat treatment time is 10 minutes in the described step 1).
4. the preparation method with titanium deoxid film of phase separation structure as claimed in claim 1 is characterized in that: the routine dose described step 2) is meant according to high polymer monomer quality 1% and adds azo-bis-isobutyl cyanide.
5. the preparation method with titanium deoxid film of phase separation structure as claimed in claim 1 is characterized in that: churning time is 30 minutes in the described step 3).
6. the preparation method with titanium deoxid film of phase separation structure as claimed in claim 1 is characterized in that: the ultraviolet light wavelength of described step 5) is 200～400 nanometers, and power is below 500W.
7. the preparation method with titanium deoxid film of phase separation structure as claimed in claim 1 is characterized in that: heat treatment time is 10 minutes in the described step 6).
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| CN2006101695573A CN101205119B (en) | 2006-12-22 | 2006-12-22 | Method for preparing titanium dioxide film with phase separation structure |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103165287A (en) * | 2013-03-08 | 2013-06-19 | 北京化工大学 | Method for manufacturing nano titanium dioxide thin film through photocuring |
| CN104478231A (en) * | 2014-11-20 | 2015-04-01 | 南阳理工学院 | Method for preparing ultraviolet-resistant TiO2 film |
-
2006
- 2006-12-22 CN CN2006101695573A patent/CN101205119B/en not_active Expired - Fee Related
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103165287A (en) * | 2013-03-08 | 2013-06-19 | 北京化工大学 | Method for manufacturing nano titanium dioxide thin film through photocuring |
| CN103165287B (en) * | 2013-03-08 | 2016-01-13 | 北京化工大学 | Photocuring prepares the method for Nano-titania Porous Films |
| CN104478231A (en) * | 2014-11-20 | 2015-04-01 | 南阳理工学院 | Method for preparing ultraviolet-resistant TiO2 film |
| CN104478231B (en) * | 2014-11-20 | 2016-08-24 | 南阳理工学院 | A kind of preventing ultraviolet TiO2the preparation method of film |
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