CN102068981B - Hydrothermal preparation method and product of film nano material with photocatalysis property - Google Patents
Hydrothermal preparation method and product of film nano material with photocatalysis property Download PDFInfo
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- CN102068981B CN102068981B CN 201010616979 CN201010616979A CN102068981B CN 102068981 B CN102068981 B CN 102068981B CN 201010616979 CN201010616979 CN 201010616979 CN 201010616979 A CN201010616979 A CN 201010616979A CN 102068981 B CN102068981 B CN 102068981B
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Abstract
The invention relates to a hydrothermal preparation method and a product of a film nano material with a photocatalysis property. The preparation method comprises the following steps of: dissolving sodium tungstate solution in a concentration modifier, wherein the modified concentration of the sodium tungstate solution is 0.1 to 1.0mol/L; allowing the sodium tungstate solution to pass through an exchange column which accommodates cation exchange resin; adding an acidity modifier into tungstic acid solution, wherein the modified pH value of the tungstic acid solution is 1.2 to 2.0; putting the tungstic acid solution into a reaction kettle and adding a matrix material simultaneously; and performing hydrothermal reaction at the temperature of between 100 and 200 DEG C for 2 to 12 hours to form the film nano material with the ultraviolet light and visible light photocatalysis property on the matrix material. The crystal structure of the film product has orthogonal and hexagonal WO3.0.33H2O mixed crystal phases and has the equal grain size of less than 30 nanometers. A prepared film has the characteristics of extremely firm bonding with a substrate, no crack and the like and is uniform; and both the two crystal phases have obvious effects on the photocatalysis property.
Description
Technical field
The present invention relates to field of material preparation, especially a kind of hydro-thermal method preparation has method and the product of the film nano material of photocatalysis performance, and the crystal structure of this nano material is WO
30.33H
2O.
Background technology
Nano-photocatalyst material has widely potentiality in the processing of polluting water and air, can be used for the aspects such as environmental protection and improvement.Nano-photocatalyst material is plated in has the self-cleaning function when forming film on the matrixes such as glass or pottery.There is defective in the film of at present existing method preparation at aspects such as fastness, uniformity and even thickness, and then affects its photo-catalysis capability.Therefore, explore a kind ofly can prepare firmly, photocatalysis film is significant to the application of catalysis material uniformly.
The multiple light catalytic film material preparation method of having invented at present concentrates on titanium dioxide, comprise: the carbon doped titanium dioxide photocatalyst has the photocatalytic activity of stability and high efficiency under visible light, the energy gap that has the visible radiation of being subjected to and excite, realize the wide range effect to visible light, can significantly improve the photo-quantum efficiency (CN 101385968A) of modifying titanium dioxide; Coating-czochralski method prepares the novel composite film material of nano titanium oxide/CNT under cryogenic conditions, have photocatalysis performance (CN 101157521A) etc. in the visible light condition.
General WO
3Energy gap be 2.8 eV, with TiO
2(3.2 eV) compares, and possesses the potentiality of photocatalysis performance.But according to band theory, only have when the conduction band position of photochemical catalyst to be higher than H
+/ H
2Oxidation-reduction potential, and valence band location is lower than O
2/ H
2During the O oxidation-reduction potential, material just has photocatalysis performance.WO
3The conduction band position be lower than H
+/ H
2Oxidation-reduction potential, thereby do not possess photocatalysis performance.The WO that has invented
3Hydrate WO
30.33H
2The O nano-powder has excellent ultraviolet light photocatalysis performance and good visible light photocatalysis ability (CN 101357330A).And TiO
2To just may make it have the visible light photocatalysis performance by modifying, with respect to WO
30.33H
2The O cost is higher, therefore studies WO
30.33H
2O has important value.
Summary of the invention
Technical problem to be solved by this invention is to provide a kind of hydro-thermal method preparation to have the method for the film nano material of photocatalysis performance, the film that makes have with substrate be combined very firmly, the characteristics such as even flawless.
Another technical problem to be solved by this invention is to provide the film nano material with photocatalysis performance of above-mentioned preparation method's acquisition.
The present invention solves the technical scheme that technique scheme takes: a kind of hydro-thermal method preparation has the method for the film nano material of photocatalysis performance, and photocatalysis performance is ultraviolet light and visible light photocatalysis performance, comprises the steps:
The first step: sodium tungstate solution is dissolved in the concentration regulator, and the concentration of sodium tungstate solution is 0.1～1.0 mol/L after regulating;
Second step: sodium tungstate solution is by filling the exchange column of cationic ion-exchange resin;
The 3rd step: add acidity regulator in sodium tungstate solution, the pH value of sodium tungstate solution is 1.2～2.0 after regulating again;
The 4th step: sodium tungstate solution is packed in the reactor, add simultaneously matrix material, after 2～12 hours, form the film nano material of ultraviolet light and visible light photocatalysis performance 100～200 ℃ of lower hydro-thermal reactions at matrix material.
Preparation method of the present invention is about having ultraviolet light and visible light photocatalysis effect, the WO that mixes mutually of quadrature and hexagonal crystal in varing proportions
30.33H
2O nanocrystalline thin film material preparation method.
Concrete, hydrothermal temperature can be 110,120,130,140,150,160,170,180,190 or 200 ℃;
The hydro-thermal reaction time can be 2,3,4,5,6,7,8,9,10,11 or 12 hours.
The concentration of sodium tungstate solution can be 0.1,0.2,0.3,0.4,0.5,0.6,0.8 or 1.0 mol/L after the concentration adjustment;
The pH value of wolframic acid solution can be 1.2,1.3,1.5,1.6,1.8 or 2.0 after the acidity adjustment;
On the basis of such scheme, in the first step, described sodium tungstate solution is the tungstate dihydrate acid sodium solution.In addition, cationic ion-exchange resin is 732 type cationic ion-exchange resins most preferably,
On the basis of such scheme, in the first step, described concentration regulator is one or more the composition in water (deionized water), ethanol, the propyl alcohol.
On the basis of such scheme, in the 3rd step, described acidity regulator is one or more the composition in acetic acid, hydrochloric acid, the hydrogen peroxide.
On the basis of such scheme, in the 3rd step, further add one or more combination of phosphoric acid, titanium salt, molysite or zinc solution, addition is 1～20ml, concentration is 0.5～2.5 mol/L.
Concrete addition can be 1,2,3,4,5,7,8,10,12,15,18 or 20ml, and concentration can be 0.5,0.8,1.0,1.2,1.5,2.0,2.2 or 2.5 mol/L.
On the basis of such scheme, described titanium salt is one or both in titanium tetrachloride, the titanium sulfate, and molysite is one or more in ferric sulfate, ferric nitrate, the ferric trichloride, and zinc salt is one or more in zinc sulfate, zinc chloride, the zinc acetate.
On the basis of such scheme, in the 4th step, described matrix material is glass or pottery.
On the basis of such scheme, the film nano material that the 4th step was obtained carries out drying under 80～120 ℃, obtains firmly uniformly nano crystal thin film material.
For the film nano material with photocatalysis performance that above-mentioned preparation method obtains, the crystal structure of described nano material is quadrature and six side WO
30.33H
2The multiphase of O, the average crystal grain yardstick is less than 30nm.
On the basis of such scheme, described WO
30.33H
2In the nanocrystalline multiphase of O, the content 10～90% of six side's phase crystal.Film is with the increase of hexagonal crystal phase content, and the visible light catalytic performance improves, and with the increase of orthorhombic crystal phase content, the ultraviolet catalytic performance improves.
The invention has the beneficial effects as follows:
Hydro-thermal method of the present invention preparation has the method for the film nano material of photocatalysis performance, the film that makes have with substrate be combined very firmly, the characteristics such as even flawless, and crystalline phase is quadrature and six side WO
30.33H
2The multiphase of O is the crystalline phase that photocatalytic is had remarkable effect, wherein, the increase of hexagonal crystal phase content, the visible light catalytic performance improves, and with the increase of orthorhombic crystal phase content, the ultraviolet catalytic performance improves.
The specific embodiment
Embodiment 1
A kind of hydro-thermal method preparation has the method for the film nano material of photocatalysis performance, and photocatalysis performance is ultraviolet light and visible light photocatalysis performance, comprises the steps:
The first step: 2.6g tungstate dihydrate acid sodium solution is dissolved in the concentration regulator 40ml deionized water, and the concentration of sodium tungstate solution is 0.2 mol/L after regulating;
Second step: the reactor of the exchange column of sodium tungstate solution by filling 732 type cationic ion-exchange resins obtains yellow solution (H
2WO
4NH
2O);
The 3rd step: add acidity regulator 1ml hydrogen peroxide in wolframic acid solution, the pH value of wolframic acid solution is 1.5 after regulating again;
The 4th step: wolframic acid solution is packed in the reactor, add simultaneously the matrix material sheet glass, after 3 hours, form WO at sheet glass 150 ℃ of lower hydro-thermal reactions
30.33H
2O nanocrystalline thin film nano material.
Its reaction is as follows:
Will be with WO
30.33H
2The glass of O nanocrystal obtains firmly uniformly WO at 100 ℃ of heat dryings
30.33H
2The O nano-crystal film.
WO on this film
30.33H
2O average crystal grain yardstick is less than 30nm, about 1.5 microns of film thickness.Wherein, six side's phase WO
30.33H
2The O crystal is about 10%, quadrature phase WO
30.33H
2The O crystal is about 90%.Under ultraviolet light (high-pressure sodium lamp) irradiation, the methyl orange degradation rate in this film nano material 2 hours reaches 57%.
Embodiment 2
A kind of hydro-thermal method preparation has the method for the film nano material of photocatalysis performance, and photocatalysis performance is ultraviolet light and visible light photocatalysis performance, comprises the steps:
The first step: 2.6g tungstate dihydrate acid sodium solution is dissolved in the concentration regulator 40ml deionized water, and the concentration of sodium tungstate solution is 0.2 mol/L after regulating;
Second step: the reactor of the exchange column of sodium tungstate solution by filling 732 type cationic ion-exchange resins obtains yellow solution (H
2WO
4NH
2O);
The 3rd step: add acidity regulator 1ml hydrogen peroxide in wolframic acid solution, the pH value of wolframic acid solution is 1.5 after regulating again, and adds the phosphoric acid solution of 3ml 1mol/L;
The 4th step: wolframic acid solution is packed in the reactor, add simultaneously the matrix material sheet glass, after 2 hours, form WO at sheet glass 180 ℃ of lower hydro-thermal reactions
30.33H
2O nanocrystalline thin film nano material.
Will be with WO
30.33H
2The glass of O nanocrystal obtains firmly uniformly WO at 80 ℃ of heat dryings
30.33H
2O film nano material.
WO on this thin-film material
30.33H
2The average crystal grain yardstick of O is less than 30nm, and thickness is about 1.2 microns.Wherein, six side's phase WO
30.33H
2The O crystal is about 50%, quadrature phase WO
30.33H
2The O crystal is about 50%.
Lower in visible light (metal halid lamp) irradiation, the methyl orange degradation rate in this film nano material 2 hours reaches 25%, and under ultraviolet light (high-pressure sodium lamp) shone, the methyl orange degradation rate in this film nano material 2 hours reached 45%.
Embodiment 3
A kind of hydro-thermal method preparation has the method for the film nano material of photocatalysis performance, and photocatalysis performance is ultraviolet light and visible light photocatalysis performance, comprises the steps:
The first step: the tungstate dihydrate acid sodium solution is dissolved in concentration regulator ethanol+deionized water, and the concentration of sodium tungstate solution is 0.3 mol/L after regulating;
Second step: the reactor of the exchange column of sodium tungstate solution by filling 732 type cationic ion-exchange resins obtains yellow solution (H
2WO
4NH
2O);
The 3rd step: add acidity regulator acetic acid in wolframic acid solution, the pH value of wolframic acid solution is 1.6 after regulating again, and adds the titanium tetrachloride solution of 2.0ml 1.5mol/L;
The 4th step: wolframic acid solution is packed in the reactor, add simultaneously the matrix material sheet glass, after 4 hours, form about 30% six side WO at sheet glass 150 ℃ of lower hydro-thermal reactions
30.33H
2O and 70% quadrature WO
30.33H
2O nanocrystalline thin film nano material.
Embodiment 4
A kind of hydro-thermal method preparation has the method for the film nano material of photocatalysis performance, and photocatalysis performance is ultraviolet light and visible light photocatalysis performance, comprises the steps:
The first step: the tungstate dihydrate acid sodium solution is dissolved in concentration regulator propyl alcohol+deionized water, and the concentration of sodium tungstate solution is 0.5 mol/L after regulating;
Second step: the reactor of the exchange column of sodium tungstate solution by filling 732 type cationic ion-exchange resins obtains yellow solution (H
2WO
4NH
2O);
The 3rd step: add acidity regulator hydrochloric acid in wolframic acid solution, the pH value of wolframic acid solution is 1.3 after regulating again, and adds the ferrum sulfuricum oxydatum solutum of 4.0ml 1.0mol/L;
The 4th step: wolframic acid solution is packed in the reactor, add simultaneously the matrix material sheet glass, after 6 hours, form about 40% six side WO at sheet glass 160 ℃ of lower hydro-thermal reactions
30.33H
2O and 60% quadrature WO
30.33H
2O nanocrystalline thin film nano material.
Embodiment 5
A kind of hydro-thermal method preparation has the method for the film nano material of photocatalysis performance, and photocatalysis performance is ultraviolet light and visible light photocatalysis performance, comprises the steps:
The first step: the tungstate dihydrate acid sodium solution is dissolved in concentration regulator ethanol+deionized water, and the concentration of sodium tungstate solution is 0.4 mol/L after regulating;
Second step: the reactor of the exchange column of sodium tungstate solution by filling 732 type cationic ion-exchange resins obtains yellow solution (H
2WO
4NH
2O);
The 3rd step: add acidity regulator acetic acid in wolframic acid solution, the pH value of wolframic acid solution is 1.6 after regulating again, and adds the solution of zinc sulfate of 5ml 2.5mol/L;
The 4th step: wolframic acid solution is packed in the reactor, add simultaneously the matrix material sheet glass, after 8 hours, form 70% six side WO at sheet glass 180 ℃ of lower hydro-thermal reactions
30.33H
2O and 30% quadrature WO
30.33H
2O nanocrystalline thin film nano material.
Above-mentioned photocatalytic activity characterizes by degraded methyl orange, and concrete operations are:
The methyl orange solution of preparation concentration 20g/L is got this concentration methyl orange solution of 15ml and is packed in the container slot, with the WO that is coated with of 25mm * 25mm
30.33H
2The glass specimen of O is immersed in the methyl orange solution.For light source, when implementing the ultraviolet catalytic test, place 20cm place, test solution top as ultraviolet source two 125W high-pressure sodium lamps; When implementing the visible light catalytic test, then a 150W Halogen lamp LED is placed 20cm place, test solution top, the while covers filter plate in the vessel port that methyl orange solution is housed, and filters out the ultraviolet light part, with this as visible light source.Fill the container of methyl orange by circulating water, and place water-bath, monitor bath temperature with temperature measurer, make the methyl orange solution temperature remain on 20 ℃ ± 2 ℃, thereby make methyl orange solution be unlikely to affect the mensuration of degradation rate owing to temperature raises.Simultaneously in methyl orange solution, pass into a small amount of air, promote the carrying out of light-catalyzed reaction.After the certain hour light-catalyzed reaction, draw 5ml methyl orange sample, place centrifuge tube, centrifugal several, getting its supernatant liquid packs in the cuvette, with the absorbance of spectrophotometer test methyl orange solution at the 483nm place, because the methyl orange concentration of dissolving in the solution is proportional to absorbance, can calculate the degradation rate of methyl orange according to the variation of absorbance.
Claims (8)
1. a hydro-thermal method preparation has the method for the film nano material of photocatalysis performance, and photocatalysis performance is ultraviolet light and visible light photocatalysis performance, it is characterized in that:
The crystal structure of described nano material is quadrature and six side WO
30.33H
2The multiphase of O, average grain size are less than 30nm, and wherein, the content of six side's phase crystal is 10～90%;
The preparation method comprises the steps:
The first step: sodium tungstate solution is dissolved in the concentration regulator, and the concentration of sodium tungstate solution is 0.1～1.0 mol/L after regulating;
Second step: sodium tungstate solution is by filling the exchange column of cationic ion-exchange resin;
The 3rd step: add acidity regulator again in wolframic acid solution, the pH value of wolframic acid solution is 1.2～2.0 after regulating;
The 4th step: wolframic acid solution is packed in the reactor, add simultaneously matrix material, after 2～12 hours, form the film nano material of ultraviolet light and visible light photocatalysis performance 100～200 ℃ of lower hydro-thermal reactions at matrix material.
2. hydro-thermal method preparation according to claim 1 has the method for the film nano material of photocatalysis performance, and it is characterized in that: in the first step, described sodium tungstate solution is the tungstate dihydrate acid sodium solution.
3. hydro-thermal method according to claim 1 preparation has the method for the film nano material of photocatalysis performance, it is characterized in that: in the first step, described concentration regulator is one or more the composition in water, ethanol, the propyl alcohol.
4. hydro-thermal method according to claim 1 preparation has the method for the film nano material of photocatalysis performance, it is characterized in that: in the 3rd step, described acidity regulator is one or more the composition in acetic acid, hydrochloric acid, the hydrogen peroxide.
5. hydro-thermal method preparation according to claim 1 has the method for the film nano material of photocatalysis performance, it is characterized in that: in the 3rd step, the combination of one or more of further adding phosphoric acid, titanium salt, molysite or zinc solution, addition is 1～20 ml, and concentration is 0.5～2.5 mol/L.
6. hydro-thermal method preparation according to claim 5 has the method for the film nano material of photocatalysis performance, it is characterized in that: described titanium salt is one or both in titanium tetrachloride, the titanium sulfate, molysite is one or more in ferric sulfate, ferric nitrate, the ferric trichloride, and zinc salt is one or more in zinc sulfate, zinc chloride, the zinc acetate.
7. hydro-thermal method preparation according to claim 1 has the method for the film nano material of photocatalysis performance, and it is characterized in that: in the 4th step, described matrix material is glass or pottery.
8. hydro-thermal method preparation according to claim 1 has the method for the film nano material of photocatalysis performance, and it is characterized in that: the film nano material that the 4th step was obtained carries out drying under 80～120 ℃, obtains firmly uniformly nano crystal thin film material.
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|---|---|---|---|---|
| CN102674463B (en) * | 2012-05-21 | 2014-01-15 | 上海交通大学 | Tungsten-base tungsten trioxide nano film, and preparation method and application thereof |
| CN103007967B (en) * | 2012-12-05 | 2014-10-29 | 上海师范大学 | BiOBr visible light catalytic thin film as well as preparation method and use thereof |
| CN107200356B (en) * | 2016-03-18 | 2019-12-17 | 纳琳威纳米科技（上海）有限公司 | preparation method of bismuth-doped tungsten oxide near-infrared high-reflection powder |
| CN105771963B (en) * | 2016-04-01 | 2018-07-17 | 东南大学 | A kind of knitting wool bulk tungsten trioxide photocatalyst and its green synthesis method |
| CN109364910B (en) * | 2018-12-14 | 2021-05-25 | 青岛大学 | Homogeneous and heterogeneous tungsten trioxide nanobelt photocatalyst and preparation method and application thereof |
| CN111348684B (en) * | 2020-03-10 | 2022-06-10 | 景德镇学院 | Preparation method and application of orthorhombic layered tungsten trioxide |
| CN113181892A (en) * | 2021-04-22 | 2021-07-30 | 浙江工商大学 | Product and method for preventing algal bloom through photocatalysis |
| CN115463652A (en) * | 2022-09-16 | 2022-12-13 | 福州大学 | Preparation method of tungsten trioxide liquid photocatalyst with antibacterial function |
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| JP5306181B2 (en) * | 2007-03-23 | 2013-10-02 | 株式会社東芝 | Method for producing tungsten trioxide powder for photocatalyst, tungsten trioxide powder for photocatalyst and photocatalyst product |
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| CN101224420A (en) * | 2008-01-22 | 2008-07-23 | 安徽大学 | Uses of light degradation catalyst tungstic oxide nano-powder |
| CN101357330A (en) * | 2008-09-03 | 2009-02-04 | 同济大学 | Photochemical catalyst nano-material for ultraviolet light and visible photocatalysis active material |
| CN101767938A (en) * | 2009-10-30 | 2010-07-07 | 陕西科技大学 | Method for preparing WO3 hydrate nanometer film |
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