CN110586072A - WO with novel structure3Micro-nano photocatalytic material - Google Patents
WO with novel structure3Micro-nano photocatalytic material Download PDFInfo
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- 230000001699 photocatalysis Effects 0.000 title claims abstract description 44
- 239000000463 material Substances 0.000 title claims abstract description 33
- 239000002244 precipitate Substances 0.000 claims abstract description 27
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 19
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 18
- 239000008367 deionised water Substances 0.000 claims abstract description 17
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 17
- 238000002360 preparation method Methods 0.000 claims abstract description 16
- 238000003756 stirring Methods 0.000 claims abstract description 15
- 238000005406 washing Methods 0.000 claims abstract description 14
- 238000000034 method Methods 0.000 claims abstract description 8
- 229910020350 Na2WO4 Inorganic materials 0.000 claims abstract description 7
- XMVONEAAOPAGAO-UHFFFAOYSA-N sodium tungstate Chemical compound [Na+].[Na+].[O-][W]([O-])(=O)=O XMVONEAAOPAGAO-UHFFFAOYSA-N 0.000 claims abstract description 7
- 238000001035 drying Methods 0.000 claims description 18
- 238000006243 chemical reaction Methods 0.000 claims description 14
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 11
- 239000000047 product Substances 0.000 claims description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- 238000005119 centrifugation Methods 0.000 claims description 7
- 238000001816 cooling Methods 0.000 claims description 5
- 238000003760 magnetic stirring Methods 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 238000010276 construction Methods 0.000 claims 6
- 239000002086 nanomaterial Substances 0.000 abstract description 17
- 239000002994 raw material Substances 0.000 abstract description 4
- 239000000126 substance Substances 0.000 abstract description 2
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 abstract 2
- 239000012535 impurity Substances 0.000 abstract 1
- 239000013067 intermediate product Substances 0.000 abstract 1
- 238000005303 weighing Methods 0.000 abstract 1
- RBTBFTRPCNLSDE-UHFFFAOYSA-N 3,7-bis(dimethylamino)phenothiazin-5-ium Chemical compound C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 RBTBFTRPCNLSDE-UHFFFAOYSA-N 0.000 description 12
- 229960000907 methylthioninium chloride Drugs 0.000 description 12
- 238000007146 photocatalysis Methods 0.000 description 9
- 239000004065 semiconductor Substances 0.000 description 9
- 238000005516 engineering process Methods 0.000 description 8
- 239000000975 dye Substances 0.000 description 7
- 238000010521 absorption reaction Methods 0.000 description 6
- 239000011941 photocatalyst Substances 0.000 description 6
- 230000015556 catabolic process Effects 0.000 description 5
- 238000006731 degradation reaction Methods 0.000 description 5
- 239000013078 crystal Substances 0.000 description 4
- 238000011160 research Methods 0.000 description 4
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 4
- 239000002057 nanoflower Substances 0.000 description 3
- 239000002073 nanorod Substances 0.000 description 3
- -1 polytetrafluoroethylene Polymers 0.000 description 3
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 3
- 239000004810 polytetrafluoroethylene Substances 0.000 description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 238000005286 illumination Methods 0.000 description 2
- 230000031700 light absorption Effects 0.000 description 2
- 239000002064 nanoplatelet Substances 0.000 description 2
- 239000002135 nanosheet Substances 0.000 description 2
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000005215 recombination Methods 0.000 description 2
- 230000006798 recombination Effects 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 238000002371 ultraviolet--visible spectrum Methods 0.000 description 2
- 241000282414 Homo sapiens Species 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000000349 field-emission scanning electron micrograph Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000006864 oxidative decomposition reaction Methods 0.000 description 1
- 239000002957 persistent organic pollutant Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 238000001338 self-assembly Methods 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
Classifications
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- A—HUMAN NECESSITIES
- A62—LIFE-SAVING; FIRE-FIGHTING
- A62D—CHEMICAL MEANS FOR EXTINGUISHING FIRES OR FOR COMBATING OR PROTECTING AGAINST HARMFUL CHEMICAL AGENTS; CHEMICAL MATERIALS FOR USE IN BREATHING APPARATUS
- A62D3/00—Processes for making harmful chemical substances harmless or less harmful, by effecting a chemical change in the substances
- A62D3/10—Processes for making harmful chemical substances harmless or less harmful, by effecting a chemical change in the substances by subjecting to electric or wave energy or particle or ionizing radiation
- A62D3/17—Processes for making harmful chemical substances harmless or less harmful, by effecting a chemical change in the substances by subjecting to electric or wave energy or particle or ionizing radiation to electromagnetic radiation, e.g. emitted by a laser
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/24—Chromium, molybdenum or tungsten
- B01J23/30—Tungsten
-
- B01J35/39—
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/10—Heat treatment in the presence of water, e.g. steam
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G41/00—Compounds of tungsten
- C01G41/02—Oxides; Hydroxides
-
- A—HUMAN NECESSITIES
- A62—LIFE-SAVING; FIRE-FIGHTING
- A62D—CHEMICAL MEANS FOR EXTINGUISHING FIRES OR FOR COMBATING OR PROTECTING AGAINST HARMFUL CHEMICAL AGENTS; CHEMICAL MATERIALS FOR USE IN BREATHING APPARATUS
- A62D2101/00—Harmful chemical substances made harmless, or less harmful, by effecting chemical change
- A62D2101/20—Organic substances
- A62D2101/26—Organic substances containing nitrogen or phosphorus
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- A—HUMAN NECESSITIES
- A62—LIFE-SAVING; FIRE-FIGHTING
- A62D—CHEMICAL MEANS FOR EXTINGUISHING FIRES OR FOR COMBATING OR PROTECTING AGAINST HARMFUL CHEMICAL AGENTS; CHEMICAL MATERIALS FOR USE IN BREATHING APPARATUS
- A62D2101/00—Harmful chemical substances made harmless, or less harmful, by effecting chemical change
- A62D2101/20—Organic substances
- A62D2101/28—Organic substances containing oxygen, sulfur, selenium or tellurium, i.e. chalcogen
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/64—Nanometer sized, i.e. from 1-100 nanometer
Abstract
The invention discloses a novel WO structure3The micro-nano photocatalytic material utilizes the principle that hydrothermal reaction substances with high temperature and high pressure are recrystallized to prepare hexagonal WO with controllable shape3And (3) micro-nano materials. With Na2WO4·2H2O and HCl are used as main raw materials, and the formed intermediate product is prepared by weighing Na with fixed quantity (3 mM) under hydrothermal condition2WO4·2H2O, 3M HCl is added in a volume of 1-5mLTaking the precipitate, adding deionized water, fully stirring, centrifugally washing the obtained light yellow precipitate to remove impurities, and dissolving the light yellow precipitate in H2O2In the preparation method, the WO with good crystallinity and uniform morphology is successfully prepared from the uniform solution at the hydrothermal temperature of 120 ℃ ~ 180 ℃ and 180 DEG C3And (3) micro-nano materials. The method of the invention comprises the following steps: simple and easy operation, easily obtained raw materials, low cost, easy popularization and the like.
Description
Technical Field
The invention belongs to the field of preparation of novel photocatalytic micro-nano structures, and relates to a prepared material for degradation of organic dyes in sewage and water purification, in particular to a novel WO structure3Micro-nano photocatalytic material.
Background
With the rapid development of modern industrial technology, a large amount of industrial three wastes, especially organic dyes, are directly discharged into the environment without being treated or treated to reach the standard, which causes huge damage to the environment and even threatens the life and health of human beings. Therefore, the treatment of organic dyes is a major problem to be solved. The traditional environment treatment technology has the problems of high energy consumption, low treatment rate, secondary pollution and the like, so that the difficulty is high when people treat the problems, and the high-speed development of the nanotechnology provides good opportunity for the application of the nanometer photocatalysis technology in recent years. The photocatalysis technology is a new technology which is developed in recent decades and has high efficiency, environmental protection and energy saving, so that the problem that the environment is difficult to solve under the normal condition can be smoothly carried out under the mild condition, and the photocatalysis technology has the characteristics of high treatment efficiency, low energy consumption, high safety and the like.
The core of the photocatalysis technology is photocatalyst, semiconductor photocatalysis is that the photocatalyst is used for generating a series of holes and free radicals with strong oxidation capability under the condition of illumination, and further carrying out oxidative decomposition reaction to degrade organic pollutants into CO2And H2And O and other inorganic matters, so that the organic matters are completely oxidized and decomposed. Its photocatalytic performance depends mainly on two factors: mobility and recombination rate of photo-generated electron-hole pairs. The positions of the valence and conduction bands of the semiconductor determine the mobility of the photo-generated electron-hole pairs, and functional groups and defects on the surface of the semiconductor have an important influence on the recombination rate of the photo-generated electron-hole pairs.
TiO was first proposed by Fujishima and Honda in Japan since 19722With Pt electrodeThe semiconductor photocatalytic material gradually becomes a key point and a hotspot of the research of the catalytic field from the theory that the photoelectric system irradiates and catalytically decomposes water under ultraviolet light to prepare hydrogen. The photocatalytic performance is one of the specific performances of semiconductors, and the photocatalysis of semiconductors is a technology for generating a series of oxidation-reduction reactions on the surfaces of semiconductors by utilizing the response process of the semiconductors to sunlight.
Common semiconductor photocatalytic materials are mainly: TiO 22、ZnO、Fe2O3、Bi2WO6And WO3Etc. so far, the most studied material has been TiO2But due to TiO2The forbidden band width of (2) is relatively large, and the conversion efficiency of visible light is low, so that people begin to improve the light utilization rate of the photocatalyst from two directions: 1. TiO 22Can be seen by visible light, and mainly uses N, S, C elements and the like to partially replace TiO2To reduce the band gap thereof; 2. develops and researches other photocatalytic materials with high-efficiency structures. In recent years, WO3The nanometer material has the features of relatively wide light absorbing band, high light stability, low cost, easy preparation, etc. and is suitable for use as secondary TiO material2And then has gained wide attention. Scientists changed WO3The influence of the photocatalyst on the photocatalytic performance is researched by taking measures such as morphology, doping or compounding.
WO3Has 5 different crystal structures: monoclinic (epsilon phase), triclinic (delta phase), monoclinic (gamma phase), orthorhombic (beta phase) and hexagonal (alpha phase). Different WO3Nanotopography to WO3The photocatalytic performance of the compound is greatly influenced, so that researchers successfully prepare WO by different physical and chemical methods3Nanorods, nanoplatelets, porous WO3Nanostructure and three-dimensional nanoflower. At present, WO3The photocatalytic performance of the porous nanostructure and the three-dimensional nanoflower is obviously improved compared with that of the nanorod and the nanosheet, but the ideal photocatalytic effect cannot be achieved, and the photocatalytic performance of the porous nanostructure and the three-dimensional nanoflower is applicable to WO with other appearances3Research into the preparation of nanomaterials is also ongoing.
From the aspect of nano material appearance design, the research utilizes Na2WO4·2H2Reaction of O and HCl to obtain light yellow precipitate and H with certain viscosity2O2Hydrothermal reaction is carried out, and under the condition of high temperature and high pressure, white products are separated out by the material in a recrystallization mode. Prepared micro-nano WO3The powder has uniform appearance, good crystallinity and stable crystal form. WO with novel structure prepared by hydrothermal method of high-pressure reaction kettle3The micro-nano material has the advantages of easily obtained raw materials, mild conditions and simple operation. WO successfully prepared by the system3The specific surface area is large, and the forbidden band width is narrow so as to be applied to the field of photocatalytic degradation of organic dyes in the future.
Disclosure of Invention
The invention aims to successfully prepare hexagonal WO assembled by regular polygons by a simple hydrothermal method3Micro-nano photocatalytic material. Preparation of WO3The size is in the micro-nano category, and the method has the advantages of good structural stability and the like, and in addition, the synthesized WO3The wider light absorption band provides possibility for the photocatalytic efficient degradation of organic dyes. The method is simple and easy to implement, convenient and fast to operate, easy to obtain raw materials, low in cost and easy to popularize.
In order to achieve the purpose, the invention adopts the following technical scheme:
WO with novel structure3The preparation method of the micro-nano photocatalytic material comprises the following steps: the method comprises the following steps:
(1) mixing Na2WO4·2H2Dissolving O in deionized water, and stirring to obtain a uniform and transparent solution;
(2) adding hydrochloric acid into the solution prepared in the step (1), and stirring to obtain a light yellow precipitate;
(3) washing the precipitate prepared in the step (2) to be clean;
(4) dissolving the washed light yellow precipitate in H2O2Magnetic stirring to obtain homogeneous transparent solution;
(5) transferring the solution obtained in the step (4) into a high-pressure reaction kettle, putting the high-pressure reaction kettle into an oven for hydrothermal reaction, and naturally cooling the high-pressure reaction kettle to room temperature after the reaction is finished;
(6) washing the precipitate obtained in the step (5) to be clean;
(7) transferring the product obtained in the step (6) into an oven for drying to obtain WO3Micro-nano photocatalytic material.
Further, in the step (1), magnetic stirring is carried out for 10-30 min.
Further, in the step (2), magnetic stirring is carried out for 30min-1 h.
Further, H of step (4)2O2The dosage of the solution (wt%: 30%) is 10-30 mL;
further, in the step (5), the hydrothermal reaction temperature is 120 ~ 180 ℃, the reaction time is 6h ~ 24h,
further, the washing mode in the steps (3) and (6) is specifically that the washing is carried out by using deionized water and absolute ethyl alcohol for 3 to 5 times in a centrifugal mode, and the centrifugal rotating speed is 3000-; centrifuging for 5-15min
Further, the drying temperature in the step (7) is 50 ~ 90 ℃, and the drying time is 10-30 h.
The invention has the following remarkable advantages: the invention starts from the synthesis angle of the material, and utilizes a hydrothermal method to prepare the self-assembled hexagon WO with uniform appearance and size3The micro-nano structure has good crystallinity, stable crystal form, simple preparation process, low synthesis cost and H2O2Direct decomposition of solvent to H under high temperature conditions2O and O2Therefore, the preparation process is more environment-friendly and sanitary; the material has wide application and can be used in a plurality of fields such as gas sensitive materials, electrochromism, photocatalysis, and the like.
WO with respect to other morphologies (e.g., nanorods, nanoplatelets)3The nano material has the following advantages:
(1) the appearance is novel: hexagonal WO formed by self-assembly of multiple regular polygonal nanosheets3The micro-nano structure has uniform size;
(2) the organic dye has a wider light absorption band, and the absorption peak position is in a visible light region (654 nm), so that the organic dye can be degraded under natural light;
(3) belongs to an orthorhombic system, has good crystallinity, stable crystal form and higher photocatalytic efficiency.
Detailed Description
Example 1
1) Adding 3mM Na2WO4·2H2Adding O into a 50mL beaker, adding 15mL deionized water for dissolving, and magnetically stirring for 20min to obtain a uniform and transparent solution;
2) preparing a 3M dilute HCl solution, dropwise adding 0.5mL of HCl solution into the solution prepared in the step (1), and magnetically stirring for 1h to prepare a light yellow precipitate;
3) centrifuging and washing the precipitate prepared in the step (2) for 3 times by using deionized water, wherein the centrifugal rotating speed is 4000r/min, and the single centrifugation time is 10 min;
4) dissolving the precipitate washed in the step (3) in 15mL of H with the mass fraction of 30%2O2Magnetically stirring for 1h to prepare a uniform and transparent solution;
5) transferring the solution into a 50mL hydrothermal reaction kettle with a polytetrafluoroethylene lining, putting the hydrothermal reaction kettle into a constant-temperature drying oven for hydrothermal reaction at 160 ℃ for 12 hours, and naturally cooling to room temperature after the reaction is finished;
6) centrifuging and washing the precipitate prepared in the step (5) by using deionized water and absolute ethyl alcohol sequentially, wherein the precipitate is washed by using the deionized water for 3 times, and washed by using the absolute ethyl alcohol for two times, the centrifugal rotating speed is 4000r/min, and the single centrifugation time is 10 min;
7) and (4) putting the centrifuged product into a drying oven for drying at the drying temperature of 80 ℃ for 24 hours to obtain a final white product.
Example 2
1) Adding 3mM Na2WO4·2H2Adding O into a 50mL beaker, adding 15mL deionized water for dissolving, and magnetically stirring for 20min to obtain a uniform and transparent solution;
2) preparing a 3M dilute HCl solution, dropwise adding 5mL of HCl solution into the solution prepared in the step (1), and magnetically stirring for 1h to prepare a light yellow precipitate;
3) centrifuging and washing the precipitate prepared in the step (2) for 3 times by using deionized water, wherein the centrifugal rotating speed is 4000r/min, and the single centrifugation time is 10 min;
4) dissolving the precipitate washed in the step (3) in 15mL of H with the mass fraction of 30%2O2Magnetically stirring for 1h to prepare a uniform and transparent solution;
5) transferring the solution into a 50mL hydrothermal reaction kettle with a polytetrafluoroethylene lining, putting the hydrothermal reaction kettle into a constant-temperature drying oven for hydrothermal reaction at 160 ℃ for 12 hours, and naturally cooling to room temperature after the reaction is finished;
6) centrifuging and washing the precipitate prepared in the step (5) by using deionized water and absolute ethyl alcohol sequentially, wherein the precipitate is washed by using the deionized water for 3 times, and washed by using the absolute ethyl alcohol for two times, the centrifugal rotating speed is 4000r/min, and the single centrifugation time is 10 min;
7) and (4) putting the centrifuged product into a drying oven for drying at the drying temperature of 80 ℃ for 24 hours to obtain a final white product.
Example 3
1) Adding 3mM Na2WO4·2H2Adding O into a 50mL beaker, adding 15mL deionized water for dissolving, and magnetically stirring for 20min to obtain a uniform and transparent solution;
2) preparing a 3M dilute HCl solution, dropwise adding 1mL of HCl solution into the solution prepared in the step (1), and magnetically stirring for 1h to prepare a light yellow precipitate;
3) centrifuging and washing the precipitate prepared in the step (2) for 3 times by using deionized water, wherein the centrifugal rotating speed is 4000r/min, and the single centrifugation time is 10 min;
4) dissolving the precipitate washed in the step (3) in 15mL of H with the mass fraction of 30%2O2Magnetically stirring for 1h to prepare a uniform and transparent solution;
5) transferring the solution into a 50mL hydrothermal reaction kettle with a polytetrafluoroethylene lining, putting the hydrothermal reaction kettle into a constant-temperature drying oven for hydrothermal reaction at 160 ℃ for 12 hours, and naturally cooling to room temperature after the reaction is finished;
6) centrifuging and washing the precipitate prepared in the step (5) by using deionized water and absolute ethyl alcohol sequentially, wherein the precipitate is washed by using the deionized water for 3 times, and washed by using the absolute ethyl alcohol for two times, the centrifugal rotating speed is 4000r/min, and the single centrifugation time is 10 min;
7) and (4) putting the centrifuged product into a drying oven for drying at the drying temperature of 80 ℃ for 24 hours to obtain a final white product.
FIG. 1 shows a hexagonal shape WO obtained in example 33FESEM image of micro-nano photocatalytic material. It can be seen from the figure that it is a hexagonal WO assembled from a number of more regular polygons3The micro-nano structure has uniform appearance and size, and the side length is about 1.5 mu m.
FIG. 2 shows a hexagonal shape WO obtained in example 33XRD spectrogram of the micro-nano photocatalytic material. The sharp WO can be seen from the spectrogram3·0.33H2The characteristic peak of O indicates that the crystallinity is good.
FIG. 3 (a) is a hexagonal WO obtained in example 33The UV-vis spectrogram of the micro-nano photocatalytic material has an absorption peak in a visible light wave band, and the position of the absorption peak is about 654nm, which shows that the appearance of WO is similar to that of the micro-nano photocatalytic material3Has strong absorption to visible light, and figure 3 (b) illustrates a hexagonal structure WO3The micro-nano material has a narrow forbidden band width of about 1.6eV, and meets the basic conditions of the photocatalytic material.
FIG. 4 (a) is a hexagonal WO made in example 33The micro-nano material is used as a photocatalyst, and UV-vis spectra of Methylene Blue (MB) solution before and after ultraviolet irradiation (the curve corresponding to 0 in the figure is that the MB solution is in WO)3Under the action of UV-vis in the dark adsorption process (30min), the ultraviolet-visible absorption peak intensity of MB is obviously reduced along with the extension of the irradiation time, which indicates that the MB is degraded; FIG. 4 (b) is a hexagonal shape WO3The photocatalytic degradation rate of the micro-nano material can be obviously found from the graph that after 2 hours of illumination, the degradation rate reaches 60.24%, and from the trend of curve rising, WO3Still having the ability to photocatalytically degrade MB, thus illustrating the hexagonal WO prepared3The micro-nano material has good photocatalytic performance.
FIGS. 5(a), (b) are WO of the novel hexagonal structure obtained in example 33Micro-nanoThe material is used as a photocatalyst, and UV-vis spectrums of Methylene Blue (MB) solutions before and after irradiation of a visible light wave band of a xenon lamp can be obviously seen: after irradiation with visible light, the absorption peak of MB at about 664nm gradually decreased, indicating that MB in the solution decreased, and it is further seen from the graph (b) that after 150min, the degradation rate of MB exceeded 90%, and after 210min, almost complete degradation (98.3%) of MB was observed, indicating that WO of the hexagonal structure3Has strong photocatalysis effect and potential application prospect in photocatalysis.
The above description is only for the preparation method of the present invention, and all equivalent changes and modifications made according to the claims of the present invention should be covered by the present invention.
Claims (7)
1. WO with novel structure3The preparation method of the micro-nano photocatalytic material is characterized by comprising the following steps: the method comprises the following steps:
1) mixing Na2WO4·2H2Dissolving O in deionized water, and stirring to obtain a uniform and transparent solution;
2) adding hydrochloric acid into the solution prepared in the step 1), and stirring to obtain a light yellow precipitate;
3) washing the precipitate prepared in the step 2) to be clean;
4) dissolving the washed light yellow precipitate in H2O2Uniformly stirring to obtain a uniform and transparent solution;
5) transferring the solution obtained in the step 4) into a high-pressure reaction kettle, putting the high-pressure reaction kettle into an oven for hydrothermal reaction, and naturally cooling the high-pressure reaction kettle to room temperature after the reaction is finished;
6) washing the precipitate obtained in the step 5) to be clean;
7) transferring the product obtained in the step 6) into an oven for drying to obtain WO3Micro-nano photocatalytic material.
2. WO of novel construction as claimed in claim 13The preparation method of the micro-nano photocatalytic material is characterized in that magnetic stirring is carried out for 10-30min in the step 1).
3. WO of novel construction as claimed in claim 13The preparation method of the micro-nano photocatalytic material is characterized in that magnetic stirring is carried out for 30min-1h in the step 2).
4. WO of novel construction as claimed in claim 13The preparation method of the micro-nano photocatalytic material is characterized in that H in the step 4)2O2The mass fraction of the solution is 30 percent.
5. WO of novel construction as claimed in claim 13The preparation method of the micro-nano photocatalytic material is characterized in that the hydrothermal reaction temperature in the step 5) is 120 ~ 180 ℃, and the reaction time is 6h ~ 24 h.
6. WO of novel construction as claimed in claim 13The preparation method of the micro-nano photocatalytic material is characterized in that the washing mode in the steps 3) and 6) is specifically that the micro-nano photocatalytic material is centrifugally washed for 3-5 times by deionized water and absolute ethyl alcohol sequentially, and the centrifugal rotating speed is 3000-; the centrifugation time is 5-15 min.
7. WO of novel construction as claimed in claim 13The preparation method of the micro-nano photocatalytic material is characterized in that the drying temperature in the step 7) is 50 ~ 90 ℃, and the drying time is 10-30 h.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN111298786A (en) * | 2020-01-07 | 2020-06-19 | 重庆化工职业学院 | Micron hexagonal prism MoO3-xPreparation method of photocatalytic material |
| CN111717936A (en) * | 2020-08-07 | 2020-09-29 | 上海应用技术大学 | Microwave intercalation preparation WO3Method of nanosheet |
| CN112499684A (en) * | 2020-12-04 | 2021-03-16 | 合肥工业大学 | Multilayer WO based on ion repulsion action dispersion stripping3Method of nanosheet |
| CN112951608A (en) * | 2021-02-04 | 2021-06-11 | 山东大学 | Ultrathin leaf type WO3Preparation method of nanosheet array photoanode |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN111298786A (en) * | 2020-01-07 | 2020-06-19 | 重庆化工职业学院 | Micron hexagonal prism MoO3-xPreparation method of photocatalytic material |
| CN111298786B (en) * | 2020-01-07 | 2024-03-12 | 重庆化工职业学院 | Micrometer hexagonal prism MoO 3-x Preparation method of photocatalytic material |
| CN111717936A (en) * | 2020-08-07 | 2020-09-29 | 上海应用技术大学 | Microwave intercalation preparation WO3Method of nanosheet |
| CN112499684A (en) * | 2020-12-04 | 2021-03-16 | 合肥工业大学 | Multilayer WO based on ion repulsion action dispersion stripping3Method of nanosheet |
| CN112951608A (en) * | 2021-02-04 | 2021-06-11 | 山东大学 | Ultrathin leaf type WO3Preparation method of nanosheet array photoanode |
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