CN103301832A - Preparation of tungsten trioxide photocatalyst in porous structure, and application of tungsten trioxide photocatalyst to sewage treatment - Google Patents
Preparation of tungsten trioxide photocatalyst in porous structure, and application of tungsten trioxide photocatalyst to sewage treatment Download PDFInfo
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- CN103301832A CN103301832A CN2013102841187A CN201310284118A CN103301832A CN 103301832 A CN103301832 A CN 103301832A CN 2013102841187 A CN2013102841187 A CN 2013102841187A CN 201310284118 A CN201310284118 A CN 201310284118A CN 103301832 A CN103301832 A CN 103301832A
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Abstract
The invention provides a method for preparing a tungsten trioxide photocatalyst in a porous structure, which belongs to the field of inorganic materials. Metal ions are adsorbed to the surface and periphery of colloidal carbon micro-spheres which serve as a template, and then the carbon micro-sphere template is removed through high-temperature calcinations to obtain a metal oxide WO3 in a porous structure. The pore passage structure has great dye degradation capacity and can be applied to light degradation of dye in industrial sewage. The WO3 in the porous structure is simple in preparation process and low in cost, and raw materials are cheap and easily available. The photocatalyst is controllable in appearance, high in chemical stability, easy to separate and free from secondary environment pollution, and is an ideal photocatalytic material.
Description
Technical field
The invention belongs to technical field of inorganic material, relate to a kind of preparation method with tungstic acid photochemical catalyst of loose structure, be mainly used in the dyestuff in the light degradation trade effluent.
Background technology
Tungstic acid (WO
3), molecular weight: 231.85, faint yellow orthorhombic system crystalline powder.Color from light to dark during heating.Proportion is 7.16g/cm
3, fusing point is 1473 ℃, boiling point is 1750 ℃, significantly distils in the time of 850 ℃, is green during fusion.Stable in the air, the water insoluble and inorganic acid except hydrofluoric acid can slowly be dissolved in ammoniacal liquor and the dense hot sodium hydroxide solution.The tungstic acid main application is the raw material as the preparation tungsten, makes carbide alloy, cutter, mould and draws tungsten filament, also can be used for powder metallurgy, also can be used for X ray screen and fire-proof fabric, and the colouring agent and the analytical reagent that are used as ware.The character of tungstic acid is different with the difference (speed and temperature) of preparation condition: the tungstic acid that makes under the low temperature is more active, and is soluble in water; The tungstic acid that high temperature makes is then water insoluble.The structure of tungstic acid depends on temperature: it is being anorthic system for rhombic system, 17 ~ 330 ℃ for monoclinic system ,-50 ~ 17 ℃ for tetragonal crystal system, 330 ~ 740 ℃ more than 740 ℃.The structure of monocline is the most common, its space group P21/n.Tungstic acid is produced the tungsten except being used for, and yellow tungstic acid also can be used as pigment, is used in pottery and the coating.
" tungstic acid photochemical catalyst preparation and use " (Chemical Industry Press, Cui Yumin, Li Huiquan, Zhang Kunzhu 2013.01.01) has mainly introduced the different preparation methods of tungstic acid, mainly contains solid phase method, liquid phase method, vapor phase method, sonochemical method.The tungstic acid of solid phase method preparation adopts the Muffle furnace calcining to form more, and its technology is simple, and still the powder that generates is easily reunited, and pattern can not get controlling preferably.Liquid phase method is usually used in the synthesis of nano crystallite, and its common feature is that raw material is based on homogeneous phase solution, behind the reaction certain hour, utilize and filter, drying, extraction waits the separation means to make solution and separated from solvent, obtain required precursor, obtain required nanoparticle in roasting.Liquid phase method mainly comprises the precipitation method, sol-gal process, hydrothermal synthesis method, microemulsion method.But the problem of hydrothermal synthesis method be equipment cost than higher, the technical costs height, complicated operation can not carry out suitability for industrialized production.The advantage of microemulsion method is that experimental provision is simple, and the product particle diameter is little and be evenly distributed, the surface-active height, and monodispersity is good, is easy to realize high purifying, has applicability widely.But it tests complex process, and the condition control ratio is harsh, and raw material is often more expensive, and loss is serious and productive rate is low, and production cost is higher relatively, has limited the practical application of this method greatly.The nano material of vapor phase method preparation has that uniform particles, purity height, particle diameter are little, good dispersion, chemical reactivity advantages of higher, but this method and technology is had relatively high expectations, plant investment is big, cost is high.Can obtain having the tungsten trioxide nano particle of rule, high-crystallinity, good dispersion under the ultrasound condition, but must in the reactant liquor that softex kw/n-butanol/cyclohexane ternary mixed system exists, generate, and not can manufacture.
Summary of the invention
The objective of the invention is at problems of the prior art, a kind of preparation method with tungstic acid photochemical catalyst of loose structure is provided.
Another object of the present invention provides a kind of tungstic acid photochemical catalyst of loose structure in Application of Sewage.
(1) the tungstic acid photochemical catalyst of loose structure
The preparation method of loose structure tungstic acid photochemical catalyst of the present invention is on the basis of high temperature solid-state method, and it is added template agent carbosphere, obtains the tungstic acid of loose structure.Comprise following processing step:
(1) preparation of colloidal-carbon microballoon: glucose fully is dissolved in distilled water, centrifugal in 120 ~ 180 ℃ of hydro-thermal reaction 6 ~ 12 h, washing, oven dry is ground, and gets brown ceramic powder shape carbosphere product;
(2) preparation of the tungstic acid photochemical catalyst of loose structure: be distributed in the distilled water colloidal-carbon microballoon powder is ultrasonic, mix with ammonium tungstate solution again, stir 12 ~ 24 h, get mixed solution; Mixed solution is heated to 60 ~ 80 ℃ then, stirring is evaporated to dried, grinds, and calcines 2 ~ 4 h then in Muffle furnace under 350 ~ 550 ℃, obtains the WO of loose structure
3Photochemical catalyst;
The concentration of ammonium tungstate solution is 0.05 ~ 0.15mol/L, and the mol ratio of ammonium tungstate and glucose is 1:160 ~ 1:320;
For carbosphere is disperseed preferably, be distributed in the distilled water its powder is ultrasonic, and with after ammonium tungstate solution mixes, carry out ultrasonic processing earlier, continue again to stir 12 ~ 24 h, get mixed solution.Ultrasonic processing is to handle 20 ~ 60 min under the ultrasonic wave of 50 ~ 100 Hz.
Describe below by SEM, XRD, thermogravimetric and ultraviolet-visible diffuse reflection characterization method structures of samples and the performance to porous pattern of the present invention.
1, SEM figure
Fig. 1 is the photochemical catalyst WO of colloidal-carbon microballoon (A), loose structure
3(B) SEM figure.From A as can be seen, the colloidal-carbon microsphere diameter of preparation is approximately 350 nm, and part is reunited, and may be because in sample making course, does not make its ultrasonic uniform scattered cause.Comparison diagram B through calcining, makes carbosphere come off as can be seen, has formed the photochemical catalyst WO with loose structure
3Material, the aperture is at 200 ~ 500 nm, and pore size differs.This pore passage structure makes it to dyestuff stronger degradation capability be arranged.
2, XRD test
Fig. 2 is the WO with loose structure
3The XRD figure of photochemical catalyst.Among Fig. 2, the angle of diffraction
The WO that belongs to monocline type at the peak of 23.12 °, 23.58 °, 24.37 ° and 34.17 ° respectively
3(002), the diffraction of (020), (200), (202) and (220) crystal face.Show when 550 ℃ of calcinings, formed monoclinic WO
3, and its diffraction maximum is sharp-pointed and do not have other impurity peaks existence, illustrates that the product crystallinity is good, and purity is higher.High degree of crystallinity can reduce the material surface defective, suppresses the compound of photo-generated carrier, thereby improves the performance of tungstic acid degradation of dye.
3, UV-vis diffuse test
Fig. 3 is loose structure photochemical catalyst WO
3Ultraviolet-visible diffuse reflection figure, as seen from Figure 3, the WO of loose structure
3Absorbing boundary corresponding energy gap about 470 nm is about 2.64 eV.Therefore, in the ultraviolet catalytic degrading waste water in the process of organic pollution, the WO of loose structure
3May possess better photocatalysis performance.
4, to the light degradation property of different dyes
Light degradation experiment: the WO that gets 50 mg loose structures
3Photochemical catalyst, dropping into initial concentration is that dark reaction 1h reaches physical absorption-desorption balance in the 50 mL different dyes solution of 10mg/L; In the irradiation down of 300 W xenon lamps (CHF-XM30-500W), per 30 min take a sample once then, and supernatant is got in centrifugation, measure the concentration of each effects of ion dyestuff with ultraviolet specrophotometer (TU-1901 type), and calculate degradation rate.Concrete outcome sees Table 1, Fig. 4.
The WO of table 1 loose structure
3Photochemical catalyst is to the light degradation property of different dyes
Above-mentioned experiment shows, the WO of the loose structure of the present invention's preparation
3Anionic dye is had stronger light degradation ability, thereby, can be used for the anionic dye in the light degradation trade effluent.
5, recycling experiment
Get 50 mg loose structure WO
3It is in the 50 Congo red solution of 10 mg/L that photochemical catalyst drops into initial concentration, after the method circulation of experiment 1 three times, measures the degradation rate to dyestuff, and the result shows, can reach more than 90 %.The WO that shows the loose structure of this present invention's preparation
3Photochemical catalyst is easy to separate, and can be recycled.
A large amount of experiments show, the proportioning ratio of ammonium tungstate and glucose, sintering temperature, roasting time etc. have certain influence to the light degradation property of porous material, and sintering temperature and roasting time have very big influence to the crystal formation of material, when sintering temperature is 550 ℃, time is 4 h, and that obtain is the WO of monocline type
3The proportioning of ammonium tungstate and glucose is to forming loose structure WO simultaneously
3Play a decisive role.Form WO
3Kong Yue many, the reactivity site that provides is more many, the light degradation ability is just more strong.
In sum, the relative prior art of the present invention has the following advantages:
1, the present invention utilizes the colloidal-carbon microballoon to be template, makes its surface and adsorbing metal ions on every side, removes the carbosphere template through high-temperature calcination then, obtains having the metal oxide WO of loose structure
3, this pore passage structure has stronger degradation capability to dyestuff, can be used for the dyestuff in the light degradation trade effluent;
2, the WO of the loose structure of the present invention's preparation
3Chemical stability is good, is easy to separate, and environment is not caused secondary pollution;
3, the WO of loose structure of the present invention
3The preparation technology of photochemical catalyst is simple, and raw material is cheap and easy to get, and cost is low; The pattern of product is by the rate of charge of glucose and ammonium tungstate, and calcining heat and time are controlled.
Description of drawings
Fig. 1 is the WO of colloidal-carbon microballoon, nano-porous structure
3The sem photograph of photochemical catalyst;
Fig. 2 is the WO of nano-porous structure
3The x-ray diffraction pattern of photochemical catalyst;
Fig. 3 is the WO of nano-porous structure
3The ultraviolet-visible diffuse reflection figure of photochemical catalyst;
Fig. 4 is the WO of nano-porous structure
3Photochemical catalyst is to the light degradation property of different dyes.
The specific embodiment
The preparation method and the performance that the present invention are had the photochemical catalyst of loose structure below by specific embodiment are done detailed explanation.
Embodiment 1
(1) preparation of colloidal-carbon microballoon: take by weighing 2g glucose, add in the 80mL distilled water, stirring is fully dissolved it, the capacity of being transferred to is in the reactor of polytetrafluoroethylene (PTFE) of 100 mL then, and 180 ℃ of following hydro-thermal reaction 12 h are centrifugal, washing, 80 ℃ of oven dry are ground, and obtain brown ceramic powder shape product and are the colloidal-carbon microballoon.
(2) nanoporous WO
3The preparation of photochemical catalyst: the carbosphere powder that takes by weighing 0.1g adds in the 40mL distilled water, ultrasonic it is fully disperseed; To the ammonium tungstate solution that wherein adds 100 mL (0.1248 mol/L), behind ultrasonic 20 min, continue to stir 24 h, get mixed solution; Then mixed solution is evaporated to driedly under 80 ℃ of stirrings, grinds, then in Muffle furnace, 550 ℃ of calcining 4 h down obtain having the WO of nano-porous structure
3Photochemical catalyst.This loose structure WO
3Light degradation property to dyestuff sees the following form:
Embodiment 2
(1) preparation of colloidal-carbon microballoon: with embodiment 1.
(2) nanoporous WO
3The preparation of photochemical catalyst: the carbosphere powder that takes by weighing 0.2 g adds in the 60mL distilled water, ultrasonic it is fully disperseed; To the ammonium tungstate solution that wherein adds 200 mL (0.1248 mol/L), behind ultrasonic 40 min, continue to stir 24 h, get mixed solution; Then mixed solution is stirred down at 80 ℃ and be evaporated to driedly, grind, then in Muffle furnace, 550 ℃ of calcining 4 h down obtain having the photochemical catalyst WO of loose structure
3This loose structure WO
3Light degradation property to dyestuff sees the following form:
Embodiment 3
(1) preparation of colloidal-carbon microballoon: with embodiment 1.
(2) nanoporous WO
3The preparation of photochemical catalyst: the carbosphere powder that takes by weighing 0.4 g adds in the 100mL distilled water, ultrasonic it is fully disperseed; To the ammonium tungstate solution that wherein adds 400 mL (0.1248 mol/L), behind ultrasonic 60 min, continue to stir 24 h again, get mixed solution; Then mixed solution is stirred down at 80 ℃ and be evaporated to driedly, grind, 550 ℃ of calcining 4 h in Muffle furnace then obtain having the photochemical catalyst WO of loose structure
3This loose structure WO
3Light degradation property to dyestuff sees the following form:
Claims (5)
1. the preparation method of loose structure tungstic acid photochemical catalyst comprises following processing step:
(1) preparation of colloidal-carbon microballoon: glucose fully is dissolved in distilled water, centrifugal in 120～180 ℃ of hydro-thermal reaction 6～12 h, washing, oven dry is ground, and gets brown ceramic powder shape carbosphere product;
(2) preparation of the tungstic acid photochemical catalyst of loose structure: be distributed in the distilled water colloidal-carbon microballoon powder is ultrasonic, mix with ammonium tungstate solution again, stir 12～24 h, get mixed solution; Mixed solution is heated to 60～80 ℃ then, stirring is evaporated to dried, grinds, and calcines 2～4 h then in Muffle furnace under 350～550 ℃, obtains the WO of loose structure
3Photochemical catalyst.
2. the preparation method of loose structure tungstic acid photochemical catalyst according to claim 1, it is characterized in that: the concentration of ammonium tungstate solution is 0.05～0.15mol/L, the mol ratio of ammonium tungstate and glucose is 1:60～1:20.
3. the preparation method of loose structure tungstic acid photochemical catalyst according to claim 1 is characterized in that: in the step (2), be distributed in the distilled water the carbosphere powder is ultrasonic, after ammonium tungstate solution mixes, carry out ultrasonic processing earlier, continue again to stir 12～24 h, get mixed solution.
4. as the preparation method of loose structure tungstic acid photochemical catalyst as described in the claim 3, it is characterized in that: described ultrasonic processing is to handle 20～60 min under the ultrasonic wave of 50～100 Hz.
5. the loose structure tungstic acid photochemical catalyst of method preparation is used for the dyestuff of light degradation trade effluent according to claim 1.
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Cited By (9)
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|---|---|---|---|---|
| CN104860355A (en) * | 2015-05-05 | 2015-08-26 | 上海应用技术学院 | Production method of large aperture of mesoporous tungsten trioxide microsphere |
| CN104874389A (en) * | 2015-05-05 | 2015-09-02 | 上海应用技术学院 | Mesoporous WO[3-x] visible-light-driven photocatalyst with oxygen vacancy as well as preparation method and application thereof |
| CN104934584A (en) * | 2015-05-13 | 2015-09-23 | 陕西科技大学 | Porous hollow WO3/WS2 nanometer material and preparation method thereof |
| CN105668638A (en) * | 2016-01-18 | 2016-06-15 | 郑州轻工业学院 | Nano-material and preparation method and application thereof |
| CN106082344A (en) * | 2016-06-15 | 2016-11-09 | 中国科学技术大学 | A kind of preparation method of the defect state Tungstic anhydride. for photocatalysis aerobic coupling |
| CN106311217A (en) * | 2016-08-19 | 2017-01-11 | 浙江师范大学 | Preparation method of Activated carbon functionalized tungsten oxide |
| CN106807359A (en) * | 2017-03-01 | 2017-06-09 | 南京信息工程大学 | A kind of simple method for preparing of the hexapetalous flower shape tungsten trioxide photocatalyst containing heterojunction structure |
| CN115931981A (en) * | 2023-01-09 | 2023-04-07 | 南方电网数字电网研究院有限公司 | Hydrogen sensor and preparation method thereof |
| CN115931981B (en) * | 2023-01-09 | 2024-04-26 | 南方电网数字电网研究院有限公司 | Hydrogen sensor and preparation method thereof |
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Non-Patent Citations (2)
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| 吕珂臻等: "WO3-TiO2复合空心球的制备及其光催化性能", 《中国有色金属学报》 * |
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Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104874389A (en) * | 2015-05-05 | 2015-09-02 | 上海应用技术学院 | Mesoporous WO[3-x] visible-light-driven photocatalyst with oxygen vacancy as well as preparation method and application thereof |
| CN104860355A (en) * | 2015-05-05 | 2015-08-26 | 上海应用技术学院 | Production method of large aperture of mesoporous tungsten trioxide microsphere |
| CN104934584B (en) * | 2015-05-13 | 2017-04-05 | 陕西科技大学 | A kind of porous hollow shell WO3/WS2Nano material and preparation method thereof |
| CN104934584A (en) * | 2015-05-13 | 2015-09-23 | 陕西科技大学 | Porous hollow WO3/WS2 nanometer material and preparation method thereof |
| US10183863B2 (en) * | 2015-05-13 | 2019-01-22 | Shaanxi University Of Science & Technology | Porous hollow shell WO3/WS2 nanomaterial and method of preparing same |
| WO2016179865A1 (en) * | 2015-05-13 | 2016-11-17 | 陕西科技大学 | Porous hollow shell wo3/ws2 nanomaterial and method of preparing same |
| CN105668638A (en) * | 2016-01-18 | 2016-06-15 | 郑州轻工业学院 | Nano-material and preparation method and application thereof |
| CN106082344B (en) * | 2016-06-15 | 2017-10-31 | 中国科学技术大学 | A kind of preparation method of defect state tungstic acid for the aerobic coupling of photocatalysis |
| CN106082344A (en) * | 2016-06-15 | 2016-11-09 | 中国科学技术大学 | A kind of preparation method of the defect state Tungstic anhydride. for photocatalysis aerobic coupling |
| CN106311217A (en) * | 2016-08-19 | 2017-01-11 | 浙江师范大学 | Preparation method of Activated carbon functionalized tungsten oxide |
| CN106311217B (en) * | 2016-08-19 | 2020-04-17 | 浙江师范大学 | Preparation method of activated carbon functionalized tungsten oxide |
| CN106807359A (en) * | 2017-03-01 | 2017-06-09 | 南京信息工程大学 | A kind of simple method for preparing of the hexapetalous flower shape tungsten trioxide photocatalyst containing heterojunction structure |
| CN115931981A (en) * | 2023-01-09 | 2023-04-07 | 南方电网数字电网研究院有限公司 | Hydrogen sensor and preparation method thereof |
| CN115931981B (en) * | 2023-01-09 | 2024-04-26 | 南方电网数字电网研究院有限公司 | Hydrogen sensor and preparation method thereof |
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Application publication date: 20130918 |