CN113101917A - Immobilized nano tungsten oxide and preparation method and application thereof - Google Patents
Immobilized nano tungsten oxide and preparation method and application thereof Download PDFInfo
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- 229910001930 tungsten oxide Inorganic materials 0.000 title claims abstract description 67
- QGLKJKCYBOYXKC-UHFFFAOYSA-N nonaoxidotritungsten Chemical compound O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 QGLKJKCYBOYXKC-UHFFFAOYSA-N 0.000 title claims abstract description 65
- 238000002360 preparation method Methods 0.000 title claims abstract description 34
- 239000000463 material Substances 0.000 claims abstract description 25
- 238000000034 method Methods 0.000 claims abstract description 20
- 239000013078 crystal Substances 0.000 claims abstract description 19
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000000758 substrate Substances 0.000 claims abstract description 13
- 229910052721 tungsten Inorganic materials 0.000 claims abstract description 13
- 239000010937 tungsten Substances 0.000 claims abstract description 13
- 238000004729 solvothermal method Methods 0.000 claims abstract description 7
- 239000011521 glass Substances 0.000 claims description 27
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 22
- 239000007810 chemical reaction solvent Substances 0.000 claims description 15
- 229920000557 Nafion® Polymers 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- 239000011248 coating agent Substances 0.000 claims description 11
- 238000000576 coating method Methods 0.000 claims description 11
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 claims description 11
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical group CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 claims description 9
- 229910001868 water Inorganic materials 0.000 claims description 9
- 238000002156 mixing Methods 0.000 claims description 8
- 238000007605 air drying Methods 0.000 claims description 6
- 238000013033 photocatalytic degradation reaction Methods 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 5
- XMVONEAAOPAGAO-UHFFFAOYSA-N sodium tungstate Chemical compound [Na+].[Na+].[O-][W]([O-])(=O)=O XMVONEAAOPAGAO-UHFFFAOYSA-N 0.000 claims description 3
- 229910021642 ultra pure water Inorganic materials 0.000 claims description 3
- 239000012498 ultrapure water Substances 0.000 claims description 3
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 2
- 239000003344 environmental pollutant Substances 0.000 claims description 2
- 231100000719 pollutant Toxicity 0.000 claims description 2
- 239000002904 solvent Substances 0.000 claims description 2
- KPGXUAIFQMJJFB-UHFFFAOYSA-H tungsten hexachloride Chemical compound Cl[W](Cl)(Cl)(Cl)(Cl)Cl KPGXUAIFQMJJFB-UHFFFAOYSA-H 0.000 claims description 2
- 230000008901 benefit Effects 0.000 abstract description 10
- 239000000843 powder Substances 0.000 abstract description 9
- 230000007547 defect Effects 0.000 abstract description 5
- 238000004064 recycling Methods 0.000 abstract description 3
- 238000009827 uniform distribution Methods 0.000 abstract description 3
- 238000010438 heat treatment Methods 0.000 abstract description 2
- 239000000047 product Substances 0.000 description 41
- 239000000243 solution Substances 0.000 description 39
- 238000006243 chemical reaction Methods 0.000 description 13
- 238000001035 drying Methods 0.000 description 12
- 238000005406 washing Methods 0.000 description 10
- 239000000725 suspension Substances 0.000 description 9
- 238000002441 X-ray diffraction Methods 0.000 description 5
- 235000019441 ethanol Nutrition 0.000 description 5
- 238000005303 weighing Methods 0.000 description 5
- 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 4
- 230000015556 catabolic process Effects 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 238000006731 degradation reaction Methods 0.000 description 4
- 239000012153 distilled water Substances 0.000 description 4
- 239000012467 final product Substances 0.000 description 4
- 229960000907 methylthioninium chloride Drugs 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 238000009210 therapy by ultrasound Methods 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000001755 magnetron sputter deposition Methods 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 238000001878 scanning electron micrograph Methods 0.000 description 3
- 238000007789 sealing Methods 0.000 description 3
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 229910003091 WCl6 Inorganic materials 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000004070 electrodeposition Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- 238000002207 thermal evaporation Methods 0.000 description 2
- 229910020350 Na2WO4 Inorganic materials 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 239000002073 nanorod Substances 0.000 description 1
- 239000002135 nanosheet Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000010979 pH adjustment Methods 0.000 description 1
- 230000001699 photocatalysis Effects 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 1
- 229910001887 tin oxide Inorganic materials 0.000 description 1
- 229910000314 transition metal oxide Inorganic materials 0.000 description 1
- UONOETXJSWQNOL-UHFFFAOYSA-N tungsten carbide Chemical compound [W+]#[C-] UONOETXJSWQNOL-UHFFFAOYSA-N 0.000 description 1
- -1 uniformly mixing Substances 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
- 238000003911 water pollution Methods 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
- 239000011787 zinc oxide Substances 0.000 description 1
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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
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/10—Photocatalysts
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W10/00—Technologies for wastewater treatment
- Y02W10/30—Wastewater or sewage treatment systems using renewable energies
- Y02W10/37—Wastewater or sewage treatment systems using renewable energies using solar energy
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Abstract
The invention provides immobilized nano tungsten oxide and a preparation method and application thereof, wherein the preparation method of the immobilized nano tungsten oxide comprises the step of providing a surface with WO3And placing the base material of the seed crystal layer in a tungsten source solution to perform a solvothermal reaction. The invention provides immobilized nano tungsten oxide and a preparation method and application thereof, the immobilized nano tungsten oxide is prepared efficiently and environmentally through a simple and easy-to-operate method, the problems that the preparation process is long and complicated, a substrate needs to be subjected to complicated treatment, the obtained product needs to be calcined, the product layer is not properly treated and is easy to fall off in the prior art are solved, and the immobilized nano tungsten oxide has the advantages of no need of independent heat treatment, mild preparation conditions, wide application range, high product controllability and the like. The obtained immobilized nano tungsten oxide product has the advantages of regular size, uniform distribution, difficult falling and easy recycling, and can effectively overcome the defects of the powder tungsten oxide in practical application.
Description
Technical Field
The invention relates to the technical field of nano materials, in particular to immobilized nano tungsten oxide and a preparation method and application thereof.
Background
Tungsten oxide is a semiconductor functional material with unique physicochemical properties, is also a cheap and stable transition metal oxide, and has been widely applied to the fields of environment, energy, life science, information technology and the like. The first research on tungsten oxide dates back to the 17 th century, WO3、NaWO3And LiWO3Etc. the artificially synthesized tungsten oxide was first studied. WO3Having multiple oxidation states, electronic structures and microstructure morphologies, which also allows WO3Has rich physicochemical property advantages, and can be widely applied to field emission equipment, photocatalytic degradation, gas sensors, electrochromic devices and other equipment.
In recent years, with the development of nanotechnology, nanometer tungsten oxide gradually enters the visual field of people, and compared with large-size tungsten oxide, the nanometer tungsten oxide has the advantages of controllable surface energy, remarkably increased specific surface area, quantum confinement effect and the like, and is specifically represented as follows: 1) a significantly increased specific surface area, which increases the surface area available for physical or chemical interaction with other substances; 2) the changed surface energy, caused by the difference in the band structure of the surface atoms and the internal bulk atoms; 3) the quantum confinement effect can significantly affect the properties of the material, such as charge transmission, electronic energy band structure, optical performance and the like, and is a phenomenon specific to nano-scale small-size materials. Therefore, the application fields of the nano tungsten oxide are more and more, and the application prospect is wide. At present, the preparation and performance characterization work of the nano tungsten oxide powder material has made great progress, and a lot of benefits are created in the practical production application, however, with the accelerated development of the practical application process, WO3Some drawbacks of the powdered photocatalytic material are gradually emerging. For example, in the process of water pollution degradation, the powder nano tungsten oxide is difficult to separate and cannot be recycled, so that tungsten resources are wasted, and secondary pollution is caused to water sources.
Among the numerous nano tungsten oxide products, the immobilized product has its own unique advantages. Compared with powder tungsten oxide, the immobilized product has the advantages of convenient recycling, environmental protection, uniform distribution, easy acquisition of an array structure and the like. The existing preparation method of the immobilized tungsten oxide mainly comprises a magnetron sputtering method, an electrochemical deposition method, a sol-gel method, a thermal evaporation method, a chemical spray thermal method and the like; however, the above methods are more limited: the preparation process is long and complicated, the substrate needs to be subjected to complicated treatment, the obtained product needs to be calcined, or the product layer is not treated properly and is easy to fall off, and the like.
Disclosure of Invention
Aiming at the defects in the prior art, the invention provides the immobilized nano tungsten oxide and a preparation method and application thereof, and the immobilized nano tungsten oxide with excellent adhesiveness is prepared in an efficient and environment-friendly manner by a simple and easy-to-operate method.
The invention adopts the following technical scheme:
the invention provides a preparation method of immobilized nano tungsten oxide, which comprises the step of providing a surface with WO3And placing the base material of the seed crystal layer in a tungsten source solution to perform a solvothermal reaction.
As mentioned above, the methods for preparing the supported nano tungsten oxide in the prior art mainly include magnetron sputtering, electrochemical deposition, sol-gel, thermal evaporation, and chemical spray thermal methods, but the above methods have the defects of long and complicated preparation process, complicated treatment of the substrate, calcination of the obtained product, or improper treatment of the product layer, and the like. The invention researches and discovers that the surface is provided with WO3The substrate material of the seed crystal layer is placed in a tungsten source solution for high-temperature and high-pressure reaction, and the immobilized nano tungsten oxide can be simply and efficiently prepared, wherein the nano tungsten oxide is uniformly distributed and is convenient to recycle, and the defects in the practical application of the powder tungsten oxide can be overcome.
Further, the surface carries WO3The preparation of the base material of the seed layer comprises: mixing WO3Dispersing in ultrapure water-ethanol solution, adding Nafion solution, mixing to obtain uniform solution, coating on substrate material, and air drying.
Preparation of surface band WO3There are various methods for the base material of the seed layer, such as magnetron sputtering, but the method proposed by the present invention is simpler and more convenient, and only WO needs to be added3Dispersing in ultrapure water-ethanol solution, adding a trace amount of Nafion (perfluorinated resin) solution, uniformly mixing, and coating on a substrate material, without large-scale equipment, thereby saving cost.
In the above technical solution, the WO3The dosage ratio of the ultrapure water to the ethanol solution is 3-30 mg/mL, preferably 10 mg/mL. In the ultrapure water-ethanol solution, the ratio of ultrapure water to ethanol is not limited, and is preferably 1:1 in volume ratio.
The dosage ratio of the Nafion solution to the ultrapure water-ethanol solution is more than 1%, preferably 5%. The Nafion solution carries WO on the prepared surface of the invention3Essential in the process of base material of the seed crystal layer, if Nafion solution is not added, WO is contained3The ultrapure water-ethanol solution cannot extend on the substrate material, so that a uniform seed crystal layer cannot be formed, and the preparation of subsequent immobilized products is seriously influenced; however, the amount of the Nafion solution added is not so large, and is preferably 5%.
The substrate material is FTO glass or ITO glass. Controlling the coating amount of the mixed solution on the substrate material to be 1-50 mu L/cm during coating2Preferably 6. mu.L/cm2。
The drying method is not limited, and the drying method can be realized by adopting the modes of room-temperature natural drying, air drying by a blower, drying by a drying oven and the like, and ensuring uniform drying.
Further, the tungsten source solution of the present invention is a mixture of a tungsten source and a reaction solvent.
The tungsten source is one or more of sodium tungstate, ammonium tungstate, tungsten hexachloride and the like.
The reaction solvent is water, alcohol or alkane solvent. When the reaction solvent is water, the reaction proceeds substantially as a hydrothermal reaction. In actual operation, the reaction solvent is reasonably selected according to the requirements on the morphology and the structure of the prepared product, and the operations of pH adjustment and the like on the reaction solvent are also allowed according to the requirements on the prepared product; similarly, the reaction conditions such as the dosage ratio of the tungsten source to the reaction solvent, the mixing time, the specification of the reaction kettle and the like are not limited and can be reasonably selected according to the requirements.
Preferably, the temperature of the solvothermal reaction is 175-185 ℃.
Preferably, WO of the base material when the solvothermal reaction is carried out3The seed layer faces downward.
In a specific embodiment of the invention, the preparation method of the immobilized nano tungsten oxide comprises the following steps:
(1) mixing WO3Dispersing in ultrapure water-ethanol solution, adding a trace amount of Nafion solution, and then carrying out ultrasonic treatment to obtain uniform milky white solution;
(2) dripping the uniform milky white solution obtained in the step (1) on FTO/ITO conductive glass, uniformly coating, and then airing to obtain the conductive glass with the seed crystal layer;
(3) dispersing a certain amount of tungsten source in a reaction solvent, uniformly mixing, transferring to a reaction kettle, adding the conductive glass with the seed crystal layer obtained in the step (2), carrying out high-temperature high-pressure reaction, and cooling to room temperature in air after the reaction is finished;
(4) and (4) collecting the conductive glass reacted in the step (3), and washing and drying to obtain a final product, namely the immobilized nano tungsten oxide.
Wherein, the conditions in the steps (1) - (3) can adopt the preferable conditions, and the washing in the step (4) refers to washing with distilled water and absolute ethyl alcohol for 1-2 times respectively, and airing treatment is carried out for about 5 minutes after each washing; the drying temperature was 60 ℃ and the atmospheric pressure was atmospheric pressure for 12 hours.
In the preparation method, when the reaction solvent is water, the obtained immobilized nano tungsten oxide is h-WO3。
When the reaction solvent is ethanol, the obtained immobilized nano tungsten oxide is m-WO3。
When the reaction solvent is n-heptane, the obtained immobilized nano tungsten oxide is o-WO3·H2O。
Further, the preparation method of the invention can also be used for preparing solid-supported products similar to metal oxide materials. For example, iron oxide, zinc oxide, tin oxide, and the like.
The invention also provides the immobilized nano tungsten oxide prepared by any one of the preparation methods.
The invention also provides application of the immobilized nano tungsten oxide in photocatalytic degradation of pollutants.
The invention provides immobilized nano tungsten oxide and a preparation method and application thereof, the immobilized nano tungsten oxide is prepared efficiently and environmentally through a simple and easy-to-operate method, the problems that the preparation process is long and complicated, a substrate needs to be subjected to complicated treatment, the obtained product needs to be calcined, the product layer is not properly treated and is easy to fall off in the prior art are solved, and the immobilized nano tungsten oxide has the advantages of no need of independent heat treatment, mild preparation conditions, wide application range, high product controllability and the like. The obtained immobilized nano tungsten oxide product has the advantages of regular size, uniform distribution, difficult falling and easy recycling, and can effectively overcome the defects of the powder tungsten oxide in practical application.
Drawings
FIG. 1 is a photographed image of the product obtained in example 1 of the present invention: (a) a seed layer, (b) a final product with a seed layer, (c) a final product without a seed layer;
FIG. 2 is an XRD pattern of the product obtained in example 1;
FIG. 3 is an SEM photograph of the product obtained in example 1;
FIG. 4 is a diagram of the photocatalytic degradation of the product obtained in example 1;
FIG. 5 is an XRD pattern of the product obtained in example 2;
FIG. 6 is an SEM photograph of the product obtained in example 2;
FIG. 7 is an XRD pattern of the product obtained in example 3;
FIG. 8 is an SEM photograph of the product obtained in example 3.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention are clearly and completely described below, and it is obvious that the described embodiments are a part of the embodiments of the present invention, but not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Unless otherwise specified, materials and reagents used in the following examples are commercially available.
Unless otherwise specified, the technical means used in the examples of the present invention are conventional means well known to those skilled in the art.
Example 1
The embodiment provides a preparation method of immobilized nano tungsten oxide, which comprises the following specific steps:
weighing 10mgWO3Dispersing the powder sample in 1mL of ultrapure water-ethanol (volume ratio is 1:1) solution, and uniformly shaking; adding 50uL of Nafion solution into the mixture, and carrying out ultrasonic treatment for 30 minutes to form uniform milky white suspension; sucking 30uL of the suspension, uniformly coating the suspension on FTO glass (1cm multiplied by 4cm), and naturally airing at room temperature to obtain the FTO glass with the seed crystal layer, as shown in (a) in figure 1.
Weigh 2.475g of Na2WO4·2H2O was dissolved in 65mL of pure water, stirred with a glass rod, and then 3.507g of NaCl was added, after which the pH of the solution was adjusted to 2, and then the solution was transferred to a 100mL autoclave. And slowly placing the FTO glass with the seed crystal layer into a high-pressure reaction kettle (the seed crystal surface faces downwards), sealing, keeping the temperature at 180 ℃ for 9 hours, and naturally cooling to room temperature after the reaction is finished. Carefully taking out the reacted conductive glass, washing the conductive glass with distilled water and absolute ethyl alcohol for 1-2 times respectively, removing unreacted residues, and carrying out air drying treatment for about 5 minutes after each washing; and (c) comparing (b) and (c), namely, the final product effect diagram is obtained after the conductive glass without the seed crystal layer is treated in the same way, and the nano tungsten oxide can be obtained on the conductive glass by using the method for preparing the seed crystal layer, while the nano tungsten oxide is hardly attached to the conductive glass in (c).
FIG. 2 is the XRD pattern of the nano-tungsten oxide product obtained in example 1, the peak value of which is shown in H-WO3And correspondingly.
Fig. 3 is an SEM image of the supported nano tungsten oxide product obtained in example 1, and it can be clearly seen that the prepared product has a uniform size distribution and a one-dimensional nanorod structure.
Fig. 4 is a graph of catalytic efficiency of photocatalytic degradation of Methylene Blue (MB) by the supported nano tungsten oxide product obtained in example 1 under visible light. The conditions for carrying out the degradation experiment are as follows: a piece of the prepared immobilized product (see FIGS. 1-3 and related descriptions for product details) was placed in 50ml MB solution (10mg/L) and subjected to catalytic degradation under visible light (λ >420nm) under 300W xenon lamp irradiation. As can be seen from FIG. 4, the catalytic degradation rate of the prepared product on MB reaches 94% at 3 h, which indicates that the product has good photocatalytic degradation performance.
Example 2
The embodiment provides a preparation method of immobilized nano tungsten oxide, which comprises the following specific steps:
weighing 10mgWO3Dispersing the powder sample in 1mL of ultrapure water-ethanol (volume ratio is 1:1) solution, and uniformly shaking; adding 50uL of Nafion solution into the mixture, and carrying out ultrasonic treatment for 30 minutes to form uniform milky white suspension; sucking 30uL of the suspension, uniformly coating the suspension on FTO glass (1cm multiplied by 4cm), and naturally airing at room temperature to obtain the FTO glass with the seed crystal layer.
Weighing 0.149g WCl6Dissolved in 50mL of ethanol solution, placed on a magnetic stirrer at 400r/min, and stirred uniformly under an air atmosphere for 4 hours, after which the solution was transferred to a 100mL autoclave. And slowly placing the FTO glass with the seed crystal layer into a high-pressure reaction kettle (the seed crystal surface faces downwards), sealing, keeping the temperature at 180 ℃ for 9 hours, and naturally cooling to room temperature after the reaction is finished. Carefully taking out the reacted conductive glass, washing the conductive glass with distilled water and absolute ethyl alcohol for 1-2 times respectively, removing unreacted residues, and carrying out air drying treatment for about 5 minutes after each washing; and (3) placing the washed product in a drying oven, and drying for 12 hours at 60 ℃ under atmospheric pressure to obtain the final immobilized nano tungsten oxide product.
FIG. 5 shows the nano-oxygen obtained in example 2XRD pattern of tungsten carbide product, its peak value and m-WO3And correspondingly.
Fig. 6 is an SEM image of the supported nano tungsten oxide product obtained in example 2, and it can be clearly seen that the prepared product has a uniform size distribution and a one-dimensional nano linear structure.
Example 3
The embodiment provides a preparation method of immobilized nano tungsten oxide, which comprises the following specific steps:
weighing 10mgWO3Dispersing the powder sample in 1mL of ultrapure water-ethanol (volume ratio is 1:1) solution, and uniformly shaking; adding 50uL of Nafion solution into the mixture, and carrying out ultrasonic treatment for 30 minutes to form uniform milky white suspension; sucking 30uL of the suspension, uniformly coating the suspension on FTO glass (1cm multiplied by 4cm), and naturally airing at room temperature to obtain the FTO glass with the seed crystal layer.
Weighing 0.149g WCl6Dissolved in 50mL of an n-heptane solution, placed on a magnetic stirrer at 400r/min, and stirred uniformly under an air atmosphere for 4 hours, after which the solution was transferred to a 100mL autoclave. And slowly placing the FTO glass with the seed crystal layer into a high-pressure reaction kettle (the seed crystal surface faces downwards), sealing, keeping the temperature at 180 ℃ for 9 hours, and naturally cooling to room temperature after the reaction is finished. Carefully taking out the reacted conductive glass, washing the conductive glass with distilled water and absolute ethyl alcohol for 1-2 times respectively, removing unreacted residues, and carrying out air drying treatment for about 5 minutes after each washing; and (3) placing the washed product in a drying oven, and drying for 12 hours at 60 ℃ under atmospheric pressure to obtain the final immobilized nano tungsten oxide product.
FIG. 7 is the XRD pattern of the nano-tungsten oxide product obtained in example 3, the peak value of which is similar to that of o-WO3·H2And O corresponds to the total weight of the catalyst.
Fig. 8 is an SEM image of the immobilized nano tungsten oxide product obtained in example 3, and it can be clearly seen that the prepared product has a uniform size distribution and a nano-sheet staggered structure.
Finally, it should be noted that: the above examples are only intended to illustrate the technical solution of the present invention, but not to limit it; although the present invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some technical features may be equivalently replaced; and such modifications or substitutions do not depart from the spirit and scope of the corresponding technical solutions of the embodiments of the present invention.
Claims (10)
1. The preparation method of the immobilized nano tungsten oxide is characterized by comprising the step of providing WO on the surface3And placing the base material of the seed crystal layer in a tungsten source solution to perform a solvothermal reaction.
2. The method for preparing the immobilized nano tungsten oxide according to claim 1, wherein the surface is provided with WO3The preparation of the base material of the seed layer comprises:
mixing WO3Dispersing in ultrapure water-ethanol solution, adding Nafion solution, mixing to obtain uniform solution, coating on substrate material, and air drying.
3. The method for preparing the immobilized nano tungsten oxide according to claim 2, wherein the WO is3The dosage ratio of the ultrapure water to the ethanol solution is 3-30 mg/mL, preferably 10 mg/mL;
and/or the dosage ratio of the Nafion solution to the ultrapure water-ethanol solution is more than 1 percent, preferably 5 percent.
4. The preparation method of the immobilized nano tungsten oxide according to claim 2 or 3, wherein the substrate material is FTO glass or ITO glass; controlling the coating amount on the substrate material to be 1-50 mu L/cm during coating2Preferably 6. mu.L/cm2。
5. The preparation method of the immobilized nano tungsten oxide according to any one of claims 1 to 4, wherein the tungsten source solution is a mixture of a tungsten source and a reaction solvent;
the tungsten source is one or more of sodium tungstate, ammonium tungstate and tungsten hexachloride;
the reaction solvent is water, alcohol or alkane solvent.
6. The preparation method of the immobilized nano tungsten oxide according to claim 5, wherein the temperature of the solvothermal reaction is 175-185 ℃.
7. The method for preparing the supported nano tungsten oxide according to claim 6, wherein WO is applied to the base material during the solvothermal reaction3The seed layer faces downward.
8. The preparation method of the immobilized nano tungsten oxide according to any one of claims 5 to 7, wherein the reaction solvent is water, and the obtained immobilized nano tungsten oxide is h-WO3；
The reaction solvent is ethanol, and the obtained immobilized nano tungsten oxide is m-WO3；
The reaction solvent is n-heptane, and the obtained immobilized nano tungsten oxide is o-WO3·H2O。
9. The immobilized nano tungsten oxide prepared by the preparation method of any one of claims 1 to 8.
10. The use of the immobilized nano tungsten oxide of claim 9 in photocatalytic degradation of pollutants.
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Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102674463A (en) * | 2012-05-21 | 2012-09-19 | 上海交通大学 | Tungsten-base tungsten trioxide nano film, and preparation method and application thereof |
| CN103708559A (en) * | 2013-12-19 | 2014-04-09 | 天津大学 | Tungsten trioxide nano-film with photocatalytic performance, and preparation method thereof |
| CN104961159A (en) * | 2015-07-09 | 2015-10-07 | 华东理工大学 | Nano-tungsten oxide, one-step vapor phase reduction preparation method of nano-tungsten oxide and application of nano-tungsten oxide |
| US20180035667A1 (en) * | 2016-08-08 | 2018-02-08 | Universiti Brunei Darussalam | Anti-bacterial and Anti-fungal Photocatalytic Coating Film and Method for Producing Thereof |
| CN109659572A (en) * | 2019-02-27 | 2019-04-19 | 中国石油大学(华东) | A kind of NiMoW nano material and preparation method thereof, a kind of hydrogen electrocatalytic oxidation catalyst electrode material and preparation method thereof |
| CN109987633A (en) * | 2017-12-29 | 2019-07-09 | 天津大学 | A kind of tungstic acid nano stick rich in Lacking oxygen, catalyst system and its preparation method and application |
| CN110078126A (en) * | 2019-03-26 | 2019-08-02 | 北京工业大学 | Solid-carrying type tungsten trioxide nano material of different-shape and its preparation method and application |
| CN111559873A (en) * | 2020-04-30 | 2020-08-21 | 北京工业大学 | Immobilized tungsten trioxide nanosheet array and preparation method and application thereof |
-
2021
- 2021-04-06 CN CN202110367629.XA patent/CN113101917B/en active Active
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102674463A (en) * | 2012-05-21 | 2012-09-19 | 上海交通大学 | Tungsten-base tungsten trioxide nano film, and preparation method and application thereof |
| CN103708559A (en) * | 2013-12-19 | 2014-04-09 | 天津大学 | Tungsten trioxide nano-film with photocatalytic performance, and preparation method thereof |
| CN104961159A (en) * | 2015-07-09 | 2015-10-07 | 华东理工大学 | Nano-tungsten oxide, one-step vapor phase reduction preparation method of nano-tungsten oxide and application of nano-tungsten oxide |
| US20180035667A1 (en) * | 2016-08-08 | 2018-02-08 | Universiti Brunei Darussalam | Anti-bacterial and Anti-fungal Photocatalytic Coating Film and Method for Producing Thereof |
| CN109987633A (en) * | 2017-12-29 | 2019-07-09 | 天津大学 | A kind of tungstic acid nano stick rich in Lacking oxygen, catalyst system and its preparation method and application |
| CN109659572A (en) * | 2019-02-27 | 2019-04-19 | 中国石油大学(华东) | A kind of NiMoW nano material and preparation method thereof, a kind of hydrogen electrocatalytic oxidation catalyst electrode material and preparation method thereof |
| CN110078126A (en) * | 2019-03-26 | 2019-08-02 | 北京工业大学 | Solid-carrying type tungsten trioxide nano material of different-shape and its preparation method and application |
| CN111559873A (en) * | 2020-04-30 | 2020-08-21 | 北京工业大学 | Immobilized tungsten trioxide nanosheet array and preparation method and application thereof |
Non-Patent Citations (1)
| Title |
|---|
| 黄倬等，冶金工业出版社, 冶金工业出版社 * |
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