CN113101917B - 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 62
- 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 58
- 238000002360 preparation method Methods 0.000 title claims abstract description 28
- 239000000463 material Substances 0.000 claims abstract description 26
- 239000000758 substrate Substances 0.000 claims abstract description 19
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims abstract description 16
- 229910052721 tungsten Inorganic materials 0.000 claims abstract description 14
- 239000010937 tungsten Substances 0.000 claims abstract description 14
- 238000004729 solvothermal method Methods 0.000 claims abstract description 7
- 239000000243 solution Substances 0.000 claims description 53
- 239000011521 glass Substances 0.000 claims description 27
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 17
- 239000007810 chemical reaction solvent Substances 0.000 claims description 16
- 229920000557 Nafion® Polymers 0.000 claims description 12
- 239000013078 crystal Substances 0.000 claims description 12
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-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
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical group CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 claims description 9
- 238000013033 photocatalytic degradation reaction Methods 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 5
- 238000007605 air drying Methods 0.000 claims description 4
- 150000001298 alcohols Chemical class 0.000 claims description 2
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 2
- 239000007864 aqueous solution Substances 0.000 claims description 2
- 239000003344 environmental pollutant Substances 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- 239000002135 nanosheet Substances 0.000 claims description 2
- 231100000719 pollutant Toxicity 0.000 claims description 2
- 239000011734 sodium Substances 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
- 229910021642 ultra pure water Inorganic materials 0.000 claims description 2
- 239000012498 ultrapure water Substances 0.000 claims description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical group C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims 1
- 229910052708 sodium Inorganic materials 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 19
- 239000000843 powder Substances 0.000 abstract description 10
- 230000007547 defect Effects 0.000 abstract description 6
- 238000001354 calcination Methods 0.000 abstract description 3
- 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 43
- 238000006243 chemical reaction Methods 0.000 description 17
- 238000001035 drying Methods 0.000 description 12
- 238000005406 washing Methods 0.000 description 10
- 238000002441 X-ray diffraction Methods 0.000 description 6
- 238000001878 scanning electron micrograph Methods 0.000 description 6
- 239000000725 suspension Substances 0.000 description 6
- 239000000126 substance Substances 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
- 235000019441 ethanol Nutrition 0.000 description 4
- 239000012467 final product Substances 0.000 description 4
- 229960000907 methylthioninium chloride Drugs 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
- 238000007789 sealing Methods 0.000 description 3
- 238000005303 weighing 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
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 238000004070 electrodeposition Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- 238000002207 thermal evaporation Methods 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 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
- -1 mixing 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
- 239000002070 nanowire 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
- 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
- XMVONEAAOPAGAO-UHFFFAOYSA-N sodium tungstate Chemical compound [Na+].[Na+].[O-][W]([O-])(=O)=O XMVONEAAOPAGAO-UHFFFAOYSA-N 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
- 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
Classifications
-
- 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—
-
- 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
-
- 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
Abstract
The invention provides a method for preparing immobilized nano tungsten oxide and application thereof, wherein the method for preparing the immobilized nano tungsten oxide comprises the steps of carrying WO on the surface 3 And placing the substrate material of the seed layer in a tungsten source solution for solvothermal reaction. The invention provides the immobilized nano tungsten oxide and the preparation method and application thereof, and the immobilized nano tungsten oxide is prepared by a simple and easy-to-operate method in a high-efficiency and environment-friendly way, so that the problems of lengthy and complex preparation process, complex treatment of a substrate, calcination treatment of an obtained product, improper treatment of a product layer, easy falling off and the like 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 regular size, uniform distribution, difficult falling and easy recycling, and can effectively overcome the defect 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 physical and chemical properties, is also an inexpensive and stable transition metal oxide, and has been widely applied to the fields of environment, energy, life science, information technology and the like. The study of tungsten oxide was traced to the earliest 17 th century, WO 3 、NaWO 3 LiWO (LiWO) 3 And the artificially synthesized tungsten oxide was first studied. WO (WO) 3 Having a variety of oxidation states, electronic structures and microstructural morphologies, which also allow WO 3 Has rich physical and chemical performance advantages and is widely applied to field emission equipment, photocatalytic degradation and gas sensitivitySensors, electrochromic devices, etc.
In recent years, with development of nano technology, nano tungsten oxide is also gradually entering into the field of view of people, and compared with large-size tungsten oxide, nano-scale tungsten oxide has the advantages of controllable surface energy, remarkably increased specific surface area, quantum confinement effect and the like, and is specifically expressed as follows: 1) A significantly increased specific surface area, which increases the surface area that can be physically or chemically reacted with other substances; 2) The changed surface energy is caused by the difference of the energy band structure of the surface atoms and the internal bulk atoms; 3) The quantum confinement effect can obviously influence the performances of charge transmission, electron energy band structure, optical performance and the like of the material, and is a phenomenon special for nanoscale small-size materials. Therefore, the application field of nano tungsten oxide is more and more, and the application prospect is wide. At present, the preparation and performance characterization of nano tungsten oxide powder materials have greatly progressed, and a lot of benefits are created in practical production and application, however, along with the accelerated development of practical application progress, WO 3 Some defects of the powder photocatalytic material are gradually revealed. 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 generated to a water source.
Among the numerous nano tungsten oxide products, the immobilized product has its own unique advantages. Compared with the 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 methods of the immobilized tungsten oxide mainly comprise 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 method is more limited: the preparation process is long and complex, the substrate needs to be subjected to complex treatment, the obtained product needs to be calcined or the product layer is improperly treated and is easy to fall off, and the like.
Disclosure of Invention
Aiming at the defects existing in the prior art, the invention provides the immobilized nano tungsten oxide and the preparation method and application thereof, and the immobilized nano tungsten oxide with excellent adhesiveness is prepared by a simple and easy-to-operate method in a high-efficiency and environment-friendly way.
The invention adopts the following technical scheme:
the invention provides a preparation method of immobilized nano tungsten oxide, which comprises the steps of carrying WO on the surface 3 And placing the substrate material of the seed layer in a tungsten source solution for solvothermal reaction.
As described above, the methods for preparing immobilized 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 lengthy and complex preparation process, complicated treatment of the substrate, calcination treatment of the obtained product, improper treatment of the product layer, and easy falling. The invention has been found to carry WO on the surface 3 The substrate material of the seed crystal layer is placed in tungsten source solution for high-temperature and high-pressure reaction, so that 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 defect in the practical application of the powder tungsten oxide can be overcome.
Further, the surface is provided with WO 3 The preparation of the base material of the seed layer includes: WO is incorporated into 3 Dispersing in ultrapure water-ethanol solution, adding Nafion solution, mixing to obtain uniform solution, coating onto substrate material, and air drying.
Preparation of the surface with WO 3 The substrate material of the seed layer can be prepared by various methods, such as magnetron sputtering, but the method is simpler and more convenient, and only WO is needed 3 Dispersing in ultrapure water-ethanol solution, adding micro Nafion (perfluorinated resin) solution, mixing, and coating onto substrate material without large-scale equipment, thereby saving cost.
In the above technical solution, said WO 3 The ratio of the amount of the aqueous solution to the ultrapure water-ethanol solution is 3 to 30mg/mL, preferably 10mg/mL. In the ultrapure water-ethanol solution, the ratio of ultrapure water to ethanol is not limited, and is preferably 1:1 by volume.
The ratio of the amount of the Nafion solution to the ultrapure water-ethanol solution is 1% or more, preferably 5%. The Nafion solution has WO on the preparation surface of the invention 3 The substrate material of the seed layer is indispensable and contains WO if Nafion solution is not added 3 The ultrapure water-ethanol solution of (2) cannot spread on the substrate material, so that a uniform seed crystal layer cannot be formed, and the preparation of subsequent immobilized products is seriously affected; however, the amount of Nafion solution added is not too large, and is preferably 5%.
The substrate material is FTO glass or ITO glass. The coating amount of the mixed solution on the substrate material is controlled to be 1-50 mu L/cm during coating 2 Preferably 6. Mu.L/cm 2 。
The method for drying is not limited, and the method can adopt the modes of natural drying at room temperature, air drying by a blower, drying by a drying box and the like, thereby ensuring uniform drying.
Further, 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, tungsten hexachloride and the like.
The reaction solvent is water, alcohols or alkanes solvent. When the reaction solvent is water, the reaction to be performed is substantially a hydrothermal reaction. In actual operation, the reaction solvent is reasonably selected according to the requirements of the morphology and structure of the prepared product, and the operations such as pH adjustment and the like of the reaction solvent are also allowed according to the requirements of the prepared product; also, the reaction conditions such as the dosage ratio of the tungsten source and the reaction solvent, the mixing time, the specification of the reaction kettle and the like are not limited, and the tungsten source and the reaction solvent are reasonably selected according to requirements.
Preferably, the solvothermal reaction temperature is 175-185 ℃.
Preferably, the WO of the base material is performed while the solvothermal reaction is performed 3 The seed layer faces downward.
In a specific embodiment of the present invention, the preparation method of the immobilized nano tungsten oxide includes the following steps:
(1) WO is incorporated into 3 Dispersing in ultrapure water-ethanol solution, adding a trace amount of Nafion solution, and performing ultrasonic treatment to obtain a uniform milky solution;
(2) Dripping the uniform milky solution obtained in the step (1) onto FTO/ITO conductive glass, coating uniformly, and airing to obtain conductive glass with a 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) into the reaction kettle, performing high-temperature high-pressure reaction, and air-cooling to room temperature after the reaction is finished;
(4) And (3) 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) to (3) can adopt the preferable conditions described above, and the washing in the step (4) means washing with distilled water and absolute ethyl alcohol for 1 to 2 times respectively, and air-drying treatment for about 5 minutes after each washing; the drying temperature was 60℃and the air 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-WO 3 。
When the reaction solvent is ethanol, the obtained immobilized nano tungsten oxide is m-WO 3 。
When the reaction solvent is n-heptane, the obtained immobilized nano tungsten oxide is o-WO 3 ·H 2 O。
Further, the preparation method of the invention can also be used for preparing the immobilized product similar to the metal oxide material. 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 the immobilized nano tungsten oxide and the preparation method and application thereof, and the immobilized nano tungsten oxide is prepared by a simple and easy-to-operate method in a high-efficiency and environment-friendly way, so that the problems of lengthy and complex preparation process, complex treatment of a substrate, calcination treatment of an obtained product, improper treatment of a product layer, easy falling off and the like 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 regular size, uniform distribution, difficult falling and easy recycling, and can effectively overcome the defect of the powder tungsten oxide in practical application.
Drawings
FIG. 1 is a photograph of the product obtained in example 1 of the present invention: (a) a seed layer, (b) a seeded final product, (c) a non-seeded final product;
FIG. 2 is an XRD pattern of the product obtained in example 1;
FIG. 3 is an SEM image of the product obtained in example 1;
FIG. 4 is a graph showing 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 image 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 image of the product obtained in example 3.
Detailed Description
For the purpose of making the objects, technical solutions and advantages of the embodiments of the present invention more clear, the technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is apparent that the described embodiments are some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
The materials and reagents used in the examples below were commercially available unless otherwise specified.
Unless specifically indicated, the technical means used in the embodiments 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 10mgWO 3 The powder sample was dispersed in 1mL of ultra pure water-ethanolIn the solution with the volume ratio of 1:1, uniformly shaking; 50uL of Nafion solution is added into the solution, and the solution is subjected to ultrasonic treatment for 30 minutes to form a uniform milky suspension; 30uL of the suspension was sucked up and uniformly applied to FTO glass (1 cm. Times.4 cm), and naturally dried at room temperature to prepare FTO glass with a seed layer, as shown in FIG. 1 (a).
Weigh 2.475g Na 2 WO 4 ·2H 2 O was dissolved in 65mL of pure water, stirred uniformly with a glass rod, 3.507g of NaCl was added, after which the pH of the solution was adjusted to ph=2, and then the solution was transferred to a 100mL autoclave. Slowly placing the FTO glass with the seed crystal layer into a high-pressure reaction kettle (with the seed crystal facing downwards), sealing, preserving heat at 180 ℃ for 9 hours, and naturally cooling to room temperature after the reaction is finished. Carefully taking out the conductive glass after the reaction, washing the conductive glass with distilled water and absolute ethyl alcohol for 1-2 times respectively, removing unreacted residues, and carrying out airing treatment for about 5 minutes after each washing; the washed product was dried in a dry oven at 60 c for 12 hours under atmospheric pressure to obtain the final immobilized nano tungsten oxide product, as shown in fig. 1 (b), where (c) in fig. 1 is a graph of the effect of the final product obtained by the same treatment of the conductive glass without the seed layer, and it is clear from comparison of (b) and (c) that nano tungsten oxide can be obtained on the conductive glass after the method for preparing the seed layer according to the present invention, and almost no nano tungsten oxide is adhered on the conductive glass in (c).
FIG. 2 shows the XRD pattern of the nano-tungsten oxide product obtained in example 1, its peak value being equal to that of h-WO 3 Corresponding to each other.
Fig. 3 is an SEM image of the immobilized 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 showing the catalytic efficiency of photocatalytic degradation of Methylene Blue (MB) in visible light of the immobilized nano-tungsten oxide product obtained in example 1. The degradation experiment was carried out as follows: a piece of the prepared immobilized product (see FIGS. 1-3 and related descriptions for product details) was placed in 50ml MB of solution (10 mg/L), and subjected to catalytic degradation under visible light (lambda >420 nm) under irradiation of a 300W xenon lamp. As can be seen from FIG. 4, the catalytic degradation rate of MB of the prepared product reaches 94% at 3 hours, 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 10mgWO 3 Dispersing the powder sample in 1mL of ultrapure water-ethanol (volume ratio is 1:1) solution, and uniformly shaking; 50uL of Nafion solution is added into the solution, and the solution is subjected to ultrasonic treatment for 30 minutes to form a uniform milky suspension; 30uL of the suspension was sucked up and uniformly applied to FTO glass (1 cm. Times.4 cm), and naturally dried at room temperature to obtain FTO glass with a seed layer.
Weigh 0.149g WCl 6 Dissolved in 50mL of ethanol solution, placed on a magnetic stirrer at 400r/min, stirred uniformly under an air atmosphere for 4 hours, after which the solution was transferred to a 100mL autoclave. Slowly placing the FTO glass with the seed crystal layer into a high-pressure reaction kettle (with the seed crystal facing downwards), sealing, preserving heat at 180 ℃ for 9 hours, and naturally cooling to room temperature after the reaction is finished. Carefully taking out the conductive glass after the reaction, washing the conductive glass with distilled water and absolute ethyl alcohol for 1-2 times respectively, removing unreacted residues, and carrying out airing treatment for about 5 minutes after each washing; and (3) placing the washed product in a drying oven, and drying at 60 ℃ for 12 hours under atmospheric pressure to obtain the final immobilized nano tungsten oxide product.
FIG. 5 is an XRD pattern of the nano-tungsten oxide product obtained in example 2, its peak value being equal to that of m-WO 3 Corresponding to each other.
Fig. 6 is an SEM image of the immobilized 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 nanowire structure.
Example 3
The embodiment provides a preparation method of immobilized nano tungsten oxide, which comprises the following specific steps:
weighing 10mgWO 3 Dispersing the powder sample in 1mL of ultrapure water-ethanol (volume ratio is 1:1) solution, and uniformly shaking; 50uL of Nafion solution is added into the solution, and the solution is subjected to ultrasonic treatment for 30 minutes to form a uniform milky suspension; sucking 30uL of the suspension, uniformly coating on FTO glass (1 cm×4 cm), and naturally drying at room temperature to obtain seed layerFTO glass.
Weigh 0.149g WCl 6 Dissolved in 50mL of 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. Slowly placing the FTO glass with the seed crystal layer into a high-pressure reaction kettle (with the seed crystal facing downwards), sealing, preserving heat at 180 ℃ for 9 hours, and naturally cooling to room temperature after the reaction is finished. Carefully taking out the conductive glass after the reaction, washing the conductive glass with distilled water and absolute ethyl alcohol for 1-2 times respectively, removing unreacted residues, and carrying out airing treatment for about 5 minutes after each washing; and (3) placing the washed product in a drying oven, and drying at 60 ℃ for 12 hours under atmospheric pressure to obtain the final immobilized nano tungsten oxide product.
FIG. 7 is an XRD pattern of the nano-tungsten oxide product obtained in example 3, its peak value corresponding to that of o-WO 3 ·H 2 O corresponds to.
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 staggered structure of nano sheets.
Finally, it should be noted that: the above embodiments are only for illustrating the technical solution of the present invention, and are not limiting; although the 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 scheme described in the foregoing embodiments can be modified or some technical features thereof can be replaced by equivalents; such modifications and substitutions do not depart from the spirit and scope of the technical solutions of the embodiments of the present invention.
Claims (6)
1. The application of the immobilized nano tungsten oxide in photocatalytic degradation of pollutants is characterized in that the preparation method of the immobilized nano tungsten oxide comprises the following steps: with the surface provided with WO 3 Placing the substrate material of the seed crystal layer in a tungsten source solution for solvothermal reaction; the immobilized nano tungsten oxide is in a one-dimensional nano rod-shaped structure, a nano linear structure or a nano sheet staggered structure; the tungsten source solution is a mixture of a tungsten source and a reaction solvent; the tungsten source is sodium tungstateOne or more of ammonium tungstate, tungsten hexachloride; the reaction solvent is water, alcohols or alkane solvents; WO for the base material when the solvothermal reaction is carried out 3 The seed crystal layer faces downwards;
said surface carrying WO 3 The preparation of the base material of the seed layer includes: WO is incorporated into 3 Dispersing in ultrapure water-ethanol solution, adding Nafion solution, mixing to obtain uniform solution, coating onto substrate material, and air drying; said WO 3 The dosage ratio of the ultra-pure water to the ethanol solution is 3-30 mg/mL; the dosage ratio of the Nafion solution to the ultrapure water-ethanol solution is 5 percent.
2. The use according to claim 1, wherein said WO 3 The dosage ratio of the aqueous solution to the ultrapure water-ethanol solution is 10mg/mL.
3. The use according to claim 1, wherein the substrate material is FTO glass or ITO glass; the coating amount on the substrate material is controlled to be 1-50 mu L/cm during coating 2 。
4. The use according to claim 3, wherein the coating amount on the substrate material is controlled to be 6 μl/cm during coating 2 。
5. The use according to claim 1, wherein the solvothermal reaction is at a temperature of 175-185 ℃.
6. The use according to claim 1, wherein the reaction solvent is water and the obtained immobilized nano tungsten oxide is h-WO 3 ；
The reaction solvent is ethanol, and the obtained immobilized nano tungsten oxide is m-WO 3 ；
The reaction solvent is n-heptane, and the obtained immobilized nano tungsten oxide is o-WO 3 ·H 2 O。
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