CN107519889B - Preparation method of copper-doped tungsten trioxide composite nanofiber material - Google Patents
Preparation method of copper-doped tungsten trioxide composite nanofiber material Download PDFInfo
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- ZNOKGRXACCSDPY-UHFFFAOYSA-N tungsten trioxide Chemical compound O=[W](=O)=O ZNOKGRXACCSDPY-UHFFFAOYSA-N 0.000 title claims abstract description 152
- 239000002121 nanofiber Substances 0.000 title claims abstract description 55
- 239000000463 material Substances 0.000 title claims abstract description 19
- 239000002131 composite material Substances 0.000 title claims abstract description 13
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 239000000243 solution Substances 0.000 claims abstract description 63
- 238000001354 calcination Methods 0.000 claims abstract description 26
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims abstract description 25
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims abstract description 25
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims abstract description 25
- 238000000034 method Methods 0.000 claims abstract description 23
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000000835 fiber Substances 0.000 claims abstract description 20
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 19
- 229910052802 copper Inorganic materials 0.000 claims abstract description 19
- 239000010949 copper Substances 0.000 claims abstract description 19
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims abstract description 15
- 238000010041 electrostatic spinning Methods 0.000 claims abstract description 15
- 239000002243 precursor Substances 0.000 claims abstract description 13
- 238000001816 cooling Methods 0.000 claims abstract description 10
- 238000002791 soaking Methods 0.000 claims abstract description 10
- 238000003756 stirring Methods 0.000 claims abstract description 10
- 150000001879 copper Chemical class 0.000 claims abstract description 7
- 239000012266 salt solution Substances 0.000 claims abstract description 5
- 239000007788 liquid Substances 0.000 claims description 8
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical group Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 4
- 238000007598 dipping method Methods 0.000 claims description 4
- 229960003280 cupric chloride Drugs 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 claims 1
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 abstract description 42
- 230000015556 catabolic process Effects 0.000 abstract description 11
- 238000006731 degradation reaction Methods 0.000 abstract description 11
- 238000013033 photocatalytic degradation reaction Methods 0.000 abstract description 7
- 238000009826 distribution Methods 0.000 abstract description 2
- 238000003911 water pollution Methods 0.000 abstract description 2
- 239000002657 fibrous material Substances 0.000 abstract 1
- 238000010438 heat treatment Methods 0.000 description 15
- 230000001699 photocatalysis Effects 0.000 description 11
- 238000001914 filtration Methods 0.000 description 8
- 239000008367 deionised water Substances 0.000 description 7
- 229910021641 deionized water Inorganic materials 0.000 description 7
- QGLKJKCYBOYXKC-UHFFFAOYSA-N nonaoxidotritungsten Chemical compound O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 QGLKJKCYBOYXKC-UHFFFAOYSA-N 0.000 description 7
- 239000011941 photocatalyst Substances 0.000 description 7
- 229910001930 tungsten oxide Inorganic materials 0.000 description 7
- 230000000694 effects Effects 0.000 description 6
- 229910021592 Copper(II) chloride Inorganic materials 0.000 description 5
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 5
- 229910001431 copper ion Inorganic materials 0.000 description 5
- 239000010842 industrial wastewater Substances 0.000 description 5
- 238000001878 scanning electron micrograph Methods 0.000 description 4
- 229910021591 Copper(I) chloride Inorganic materials 0.000 description 3
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- PYWVYCXTNDRMGF-UHFFFAOYSA-N rhodamine B Chemical compound [Cl-].C=12C=CC(=[N+](CC)CC)C=C2OC2=CC(N(CC)CC)=CC=C2C=1C1=CC=CC=C1C(O)=O PYWVYCXTNDRMGF-UHFFFAOYSA-N 0.000 description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 230000000593 degrading effect Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 206010007269 Carcinogenicity Diseases 0.000 description 1
- 208000012886 Vertigo Diseases 0.000 description 1
- 238000002835 absorbance Methods 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000008280 blood Substances 0.000 description 1
- 210000004369 blood Anatomy 0.000 description 1
- 230000007670 carcinogenicity Effects 0.000 description 1
- 231100000260 carcinogenicity Toxicity 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000004043 dyeing Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 238000002715 modification method Methods 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000002957 persistent organic pollutant Substances 0.000 description 1
- 238000007146 photocatalysis Methods 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
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- 238000001179 sorption measurement Methods 0.000 description 1
- 238000009987 spinning Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000005641 tunneling Effects 0.000 description 1
- 238000000870 ultraviolet spectroscopy Methods 0.000 description 1
- 239000002351 wastewater 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
- 239000011787 zinc oxide Substances 0.000 description 1
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- 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
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/85—Chromium, molybdenum or tungsten
- B01J23/888—Tungsten
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- C—CHEMISTRY; METALLURGY
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Abstract
The invention discloses a preparation method of a copper-doped tungsten trioxide composite nanofiber material, which comprises the following steps: s1, dissolving ammonium metatungstate in water, adding polyvinylpyrrolidone, and stirring to obtain a precursor solution; s2, performing electrostatic spinning on the precursor solution in the S1 to obtain a primary spun fiber; s3, calcining the spun fiber prepared in the S2, and cooling to obtain tungsten trioxide nano fiber; s4, soaking the tungsten trioxide nano-fibers in the S3 in a copper salt solution, and calcining to obtain the fiber material. The method provided by the invention is simple and easy to implement, the parameters can be accurately controlled, the cost is low, and the method is green and environment-friendly; the prepared copper-doped tungsten trioxide composite nanofiber has the advantages of uniform diameter distribution, large length-diameter ratio and stable appearance, and meanwhile, the copper doping greatly improves the photocatalytic degradation performance of tungsten trioxide, has excellent aniline degradation performance, and has great application prospect in the field of water pollution.
Description
Technical Field
The invention belongs to the technical field of nano materials, and particularly relates to a preparation method of a copper-doped tungsten trioxide composite nano fiber material.
Background
In recent years, with increasingly serious environmental problems and the demand for new energy in human society development, the photocatalytic technology has attracted attention due to its wide application prospect. The photocatalysis technology can completely decompose various organic pollutants by directly utilizing sunlight at room temperature, has no secondary pollution, and becomes one of an ideal environmental pollution treatment technology and the most active research fields at home and abroad.
Compared with common photocatalysts such as titanium dioxide and zinc oxide, the tungsten trioxide has a small forbidden band width (about 2.5-2.8 eV) and a large light absorption range, can more effectively utilize visible light which accounts for nearly half of solar radiation energy, and has a significant volume effect, surface effect, quantum size effect and macroscopic quantum tunneling effect. Therefore, the photocatalyst has attracted attention as a novel photocatalyst in recent years. However, the single tungsten trioxide has relatively low photocatalytic activity, has the defects of photo-corrosion, low utilization rate of visible light and the like, and is difficult to obtain stable and efficient photocatalytic capability. The existing research shows that metal ions are doped into the semiconductor photocatalyst, the recombination of electron-hole pairs can be obviously inhibited through the IFCT effect, and the catalytic activity of the photocatalyst is improved. The copper element is widely distributed on the earth, is cheap and easily available, and does not cause secondary pollution to water, so that the copper ion doping modification of the tungsten trioxide has obvious advantages for the photocatalytic application of the tungsten trioxide.
Aniline is one of the most important amine substances, occupies a large proportion in industrial wastewater pollutants, can reduce the oxygen carrying capacity of blood, has strong toxicity and carcinogenicity, and is difficult to degrade. At present, the concentration standard of aniline in industrial wastewater discharge in China is 1 mg/L-5 mg/L, but how to completely degrade aniline in wastewater as far as possible is still a goal pursued by researchers.
Disclosure of Invention
The invention aims to provide a preparation method of a copper-doped tungsten trioxide composite nanofiber material.
Specifically, the invention aims to design and provide a modification method for copper doping of electrostatic spinning tungsten trioxide nano-fibers, so as to improve the photocatalytic performance of the tungsten trioxide nano-fibers, and the prepared photocatalyst is used for degrading aniline solution.
The copper ion doped tungsten trioxide nanofiber material provided by the invention is not only used for photocatalytic degradation of dye reagents such as rhodamine and the like, but also can be directly applied to degradation of aniline solution.
The purpose of the invention is realized by the following technical scheme:
the invention provides a preparation method of a copper-doped tungsten trioxide composite nanofiber material, which comprises the following steps:
s1, dissolving ammonium metatungstate in water, adding polyvinylpyrrolidone, and stirring to obtain a precursor solution;
s2, performing electrostatic spinning on the precursor solution in the S1 to obtain a primary spun fiber;
s3, calcining the spun fiber prepared in the S2, and cooling to obtain tungsten trioxide nano fiber;
s4, soaking the tungsten trioxide nano-fibers in the S3 in a copper salt solution, and calcining to obtain the material;
in S1, the solid-to-liquid ratio of ammonium metatungstate to water is (0.2-0.8) to 1, and the molecular weight of polyvinylpyrrolidone is (1-2) × 106(ii) a The solid-liquid ratio of the polyvinylpyrrolidone to the water is (0.1-0.5): 1;
s2, in the step of electrostatic spinning, the voltage is 16-25 KV, the receiving distance is 12cm, and the advancing speed is 0.005-0.1 ml/min;
in S4, the concentration of the copper salt solution is 1.0-6.0 g/L, and the mass fraction of copper relative to tungsten trioxide is 1-5%.
Preferably, the mass fraction of copper relative to tungsten trioxide is 2%.
Preferably, the molecular weight of polyvinylpyrrolidone in S1 is 1.3 × 106。
Preferably, in S1, the solid-to-liquid ratio of ammonium metatungstate to water is (0.5-0.6): 1; the solid-liquid ratio of the polyvinylpyrrolidone to the water is (0.2-0.4): 1.
preferably, the calcination temperature in S3 is 500-650 ℃, the temperature rising speed is 1-5 ℃/min, and the temperature is kept for 2-4 hours.
Preferably, the dipping temperature in S4 is 80-90 ℃, and the dipping time is 0.5-3 hours.
Preferably, the calcining temperature in S4 is 600-700 ℃, and the calcining time is 1-3 h.
Preferably, the copper salt in S4 is copper chloride.
The invention also protects the copper-doped tungsten trioxide composite nanofiber material prepared by the preparation method.
Further, the invention protects the application of the copper-doped tungsten trioxide composite nanofiber material in water body pollution.
The copper-doped tungsten trioxide prepared by the method does not change the nanofiber structure of the tungsten trioxide, has stable appearance, and greatly improves the photocatalytic degradation performance of the tungsten trioxide; meanwhile, aniline, a main raw material of industrial wastewater, has strong photocatalytic performance, and can be degraded to be lower than the highest requirement of domestic discharge standard.
Compared with the prior art, the invention has the following advantages and beneficial effects:
the method provided by the invention is simple and easy to implement, the parameters can be accurately controlled, the cost is low, and the method is green and environment-friendly; the prepared copper-doped tungsten trioxide composite nanofiber has the advantages of uniform diameter distribution, large length-diameter ratio and stable appearance, and meanwhile, the copper doping greatly improves the photocatalytic degradation performance of tungsten trioxide, has excellent aniline degradation performance, and has great application prospect in the field of water pollution.
Drawings
Figure 1 is an SEM image of the tungsten trioxide nanofibers produced and tungsten trioxide after copper doping.
Figure 2 is an XRD pattern of tungsten trioxide nanofibers made using the method of the present invention and tungsten trioxide after copper doping.
FIG. 3 is a graph showing the degradation effect of rhodamine-simulated industrial wastewater by using copper-doped tungsten trioxide and pure tungsten trioxide prepared by the method of the present invention as catalysts.
Fig. 4 is a graph showing the degradation of aniline by using the copper-doped tungsten trioxide material provided by the present invention.
Detailed Description
The present invention will be further described with reference to the following specific examples and drawings, which are not intended to limit the invention in any manner. Reagents, methods and apparatus used in the present invention are conventional in the art unless otherwise indicated.
Unless otherwise indicated, reagents and materials used in the present invention are commercially available.
The method takes ammonium metatungstate and copper chloride as main raw materials, prepares the copper-doped tungsten trioxide nano-fiber by using an electrostatic spinning method and an immersion method, and directly uses the copper-doped tungsten trioxide nano-fiber as a photocatalyst for degrading aniline solution.
Example 1:
dissolving 2.5g of commercially available ammonium metatungstate in 5ml of deionized water, adding polyvinylpyrrolidone (PVP) with the molecular weight of 1300000, wherein the addition amount is 1g, and stirring until the solution is uniform and transparent to obtain a precursor solution; then, a single-shaft electrostatic spinning method is adopted, the voltage is 20KV, the receiving distance is 12cm, the propelling speed is 0.02ml/min, and white cloth-shaped primary spinning fibers are obtained; and (3) calcining the spun fiber in a muffle furnace at 600 ℃, keeping the temperature for 3 hours at the heating speed of 5 ℃/min, and naturally cooling to room temperature to obtain the tungsten trioxide nanofiber. Preparing 1.05g/L CuCl2And taking 10ml of the solution, adding 0.5g of tungsten oxide nano fiber into the solution, soaking the solution on a heating table at 90 ℃ for 1 hour, filtering the solution, and finally calcining the solution for 2 hours in a muffle furnace at 650 ℃ for two times to obtain the 1% copper-doped tungsten trioxide nano fiber.
Example 2:
dissolving 3.5g of ammonium metatungstate hydrate in 5ml of deionized water, adding polyvinylpyrrolidone (PVP) with the molecular weight of 1300000, wherein the addition amount is 1.5g, and stirring until the solution is uniform and transparent to obtain a precursor solution; then, obtaining the spun fiber by a uniaxial electrostatic spinning method, wherein the voltage is 20KV, the receiving distance is 12cm, and the propelling speed is 0.02 ml/min; and (3) calcining the spun fiber in a muffle furnace at 650 ℃, keeping the temperature for 3 hours at the heating speed of 5 ℃/min, and naturally cooling to room temperature to obtain the tungsten trioxide nanofiber. 2.1g/L CuCl is prepared2Taking 10ml of the solution, adding 0.5g of tungsten oxide nano-fiber into the solution, and placing the solution on a heating tableSoaking at 85 ℃ for 1 hour, filtering, and finally calcining for 3 hours in a muffle furnace at 650 ℃ for the second time to obtain the 2% copper-doped tungsten trioxide nano-fiber.
Example 3:
dissolving 3.0g of ammonium metatungstate hydrate in 5ml of deionized water, adding polyvinylpyrrolidone (PVP) with the molecular weight of 1300000, wherein the addition amount is 1.5g, and stirring until the solution is uniform and transparent to obtain a precursor solution; then, obtaining the spun fiber by a uniaxial electrostatic spinning method, wherein the voltage is 24KV, the receiving distance is 12cm, and the propelling speed is 0.02 ml/min; and (3) calcining the spun fiber in a muffle furnace at 550 ℃, keeping the temperature for 3 hours at the heating speed of 5 ℃/min, and naturally cooling to room temperature to obtain the tungsten trioxide nanofiber. Preparing 3.15g/L CuCl2And (3) taking 10ml of the solution, adding 0.5g of tungsten oxide nano fiber, soaking the solution on a heating table at 80 ℃ for 1 hour, filtering the solution, and finally carrying out secondary calcination in a muffle furnace at 650 ℃ for 3 hours to obtain the tungsten trioxide nano fiber doped with 3% copper.
Example 4:
dissolving 2.5g of ammonium metatungstate hydrate in 5ml of deionized water, adding polyvinylpyrrolidone (PVP) with the molecular weight of 1300000, wherein the addition amount is 2.0g, and stirring until the solution is uniform and transparent to obtain a precursor solution; then, obtaining the spun fiber by a uniaxial electrostatic spinning method, wherein the voltage is 24KV, the receiving distance is 12cm, and the propelling speed is 0.05 ml/min; and (3) calcining the spun fiber in a muffle furnace at 650 ℃, keeping the temperature for 3 hours at the heating speed of 5 ℃/min, and naturally cooling to room temperature to obtain the tungsten trioxide nanofiber. 4.2g/L CuCl is prepared2And taking 10ml of the solution, adding 0.5g of tungsten oxide nano fiber into the solution, soaking the solution on a heating table at 85 ℃ for 1 hour, filtering the solution, and finally calcining the solution for 1 hour in a muffle furnace at 650 ℃ for two times to obtain the 4% copper-doped tungsten trioxide nano fiber.
Example 5:
dissolving 2.5g of ammonium metatungstate hydrate in 5ml of deionized water, adding polyvinylpyrrolidone (PVP) with the molecular weight of 1300000, wherein the addition amount is 1.0g, and stirring until the solution is uniform and transparent to obtain a precursor solution; then, obtaining the spun fiber by a uniaxial electrostatic spinning method, wherein the voltage is 20KV, the receiving distance is 12cm, and the propelling speed is 0.05 ml/min; placing the spun fiber inCalcining at 650 ℃ in a muffle furnace at the heating rate of 5 ℃/min, preserving heat for 3 hours, and naturally cooling to room temperature to obtain the tungsten trioxide nano-fiber. Preparing 5.25g/L CuCl2And taking 50ml of the solution, adding 0.5g of tungsten oxide nano-fiber into the solution, soaking the solution on a heating table at 90 ℃ for 3 hours, filtering the solution, and finally calcining the solution for 3 hours in a muffle furnace at 650 ℃ for two times to obtain the 5% trace copper doped tungsten trioxide nano-fiber.
Comparative example 1:
dissolving 2.5g of ammonium metatungstate hydrate in 5ml of deionized water, adding polyvinylpyrrolidone (PVP) with the molecular weight of 1300000, wherein the addition amount is 1.0g, and stirring until the solution is uniform and transparent to obtain a precursor solution; then, obtaining the spun fiber by a uniaxial electrostatic spinning method, wherein the voltage is 20KV, the receiving distance is 12cm, and the propelling speed is 0.05 ml/min; and (3) calcining the spun fiber in a muffle furnace at 650 ℃, keeping the temperature for 3 hours at the heating speed of 5 ℃/min, and naturally cooling to room temperature to obtain the tungsten trioxide nanofiber. Preparing 5.25g/L CuCl2Taking 50ml of the solution, adding 0.5g of tungsten oxide nano-fiber, soaking the solution on a heating table at 90 ℃ for 30min, filtering, and finally calcining the solution for 3 hours in a muffle furnace at 650 ℃ for two times, wherein the obtained sample is the tungsten trioxide nano-fiber doped with copper, but only a very small amount of copper ions are loaded on the surface of the nano-fiber due to too short impregnation time.
Comparative example 2:
dissolving 2.5g of ammonium metatungstate hydrate in 5ml of deionized water, adding polyvinylpyrrolidone (PVP) with the molecular weight of 1300000, wherein the addition amount is 1.0g, and stirring until the solution is uniform and transparent to obtain a precursor solution; then, obtaining the spun fiber by a uniaxial electrostatic spinning method, wherein the voltage is 20KV, the receiving distance is 12cm, and the propelling speed is 0.05 ml/min; and (3) calcining the spun fiber in a muffle furnace at 650 ℃, keeping the temperature for 3 hours at the heating speed of 5 ℃/min, and naturally cooling to room temperature to obtain the tungsten trioxide nanofiber. Preparing 50 g/L CuCl2And (3) taking 50ml of the solution, adding 0.5g of tungsten oxide nano fiber, soaking the solution on a heating table at 90 ℃ for 3 hours, filtering the solution, and finally calcining the solution in a muffle furnace at 650 ℃ for 3 hours to obtain the excessive copper-doped tungsten trioxide nano fiber. The test of the photocatalytic degradation of aniline is carried out, and the aniline can be irradiated for 3 hoursAnd the concentration of the aniline solution is degraded from 5mg/L to 2.3mg/L, and the photocatalytic activity of the tungsten trioxide nano-fibers is reduced.
Comparative example 3:
using a commercially available ordinary tungsten trioxide powder, 5.25g/L of CuCl was prepared2Taking 50ml of the solution, adding 0.5g of tungsten trioxide, soaking the solution on a heating table at 90 ℃ for 30min, filtering, and finally calcining the solution for 3 hours in a muffle furnace at 650 ℃ to obtain trace copper-doped tungsten trioxide powder, carrying out an experiment on the powder for photocatalytic degradation of aniline, wherein the concentration of the aniline solution is degraded from 5mg/L to 2.8mg/L under the irradiation of visible light for 3 hours, and the photocatalytic activity of the aniline solution is obviously lower than that of a material prepared by doping copper ions in tungsten trioxide nano-fibers prepared by electrostatic spinning.
In which fig. 1 is an SEM image of the material produced in example 1, and fig. 1 (a) is an SEM image of the tungsten trioxide nanofiber produced. Fig. 1 (b) is an SEM image after the copper doping treatment. It can be seen that the copper doping treatment did not affect the surface morphology of the tungsten trioxide nanofibers.
Figure 2 is an XRD pattern of pure tungsten trioxide and doped tungsten trioxide based on different copper contents prepared using the process of the present invention in example 1. In fig. 2, peaks at diffraction angles of 23.1, 23.5, 24.3, 26.5, 28.9, 33.2, 34.1 and 41.9 ° belong to the diffraction of monoclinic tungsten trioxide (002), (020), (200), (120), (112), (022), (202) and (222) crystal planes, respectively. It can be seen that the product produced was tungsten trioxide, and the crystallinity was good. The diffraction peak is not changed after copper doping, and the crystal structure of the tungsten trioxide is not changed after a small amount of copper is doped.
FIG. 3 is a graph showing the degradation effect of rhodamine-simulated industrial wastewater by using copper-doped tungsten trioxide and pure tungsten trioxide prepared by the method of the present invention as catalysts. After copper ion doping, the photocatalytic activity of tungsten trioxide is obviously improved, and the degradation rate of rhodamine can reach 48.87%, 70.33%, 84.18%, 58.12%, 35.35% and 41.17% in 3 hours.
FIG. 4 is a graph showing the photocatalytic degradation performance of aniline using the material provided by the embodiment of the present invention. The selection of the sample used was based on the degradation results for rhodamine in fig. 3, using 2% copper doped tungsten trioxide nanofibers with the strongest photocatalytic activity. The degradation of aniline was performed as follows:
adding 150ml aniline solution with the concentration of 5mg/L into a reactor, putting 50mg prepared tungsten trioxide nano-fibers or copper-doped tungsten trioxide into the aniline solution, carrying out dark reaction for 30min to reach adsorption equilibrium, then irradiating under a 300W xenon lamp, taking a sample every 30min, carrying out dyeing treatment on the solution according to the method in GB 11889-1989, measuring absorbance by using an ultraviolet-visible spectrophotometer and calculating the degradation rate of the solution. The degradation result is shown in figure 4, and the aniline solution can be reduced from 5mg/L to 0.658mg/L after being irradiated by light for three hours, which is far lower than the lowest detection concentration of 1mg/L established in the present state.
The above-mentioned embodiments are intended to illustrate the objects, technical solutions and advantages of the present invention in further detail, and it should be understood that the above-mentioned embodiments are merely exemplary embodiments of the present invention, and are not intended to limit the scope of the present invention, and any modifications, equivalent substitutions, improvements and the like made within the spirit and principle of the present invention should be included in the scope of the present invention.
Claims (9)
1. A preparation method of a copper-doped tungsten trioxide composite nanofiber material is characterized by comprising the following steps:
s1, dissolving ammonium metatungstate in water, adding polyvinylpyrrolidone, and stirring to obtain a precursor solution;
s2, performing electrostatic spinning on the precursor solution in the S1 to obtain a primary spun fiber;
s3, calcining the spun fiber prepared in the S2, and cooling to obtain tungsten trioxide nano fiber;
s4, soaking the tungsten trioxide nano-fibers in the S3 in a copper salt solution, and calcining to obtain the material;
in S1, the solid-to-liquid ratio of ammonium metatungstate to water is (0.2-0.8): 1g/ml, and the molecular weight of polyvinylpyrrolidone is (1-2) × 106(ii) a The solid-liquid ratio of the polyvinylpyrrolidone to the water is (0.1-0.5):1g/ml；
s2, in the step of electrostatic spinning, the voltage is 16-25 KV, the receiving distance is 12cm, and the advancing speed is 0.005-0.1 ml/min; in S4, the copper salt is cupric chloride; the concentration of the copper salt solution is 1.0-6.0 g/L, and the mass fraction of copper relative to tungsten trioxide is 1-5%.
2. The production method according to claim 1, wherein the mass fraction of copper with respect to tungsten trioxide is 2%.
3. The method according to claim 1, wherein the polyvinylpyrrolidone in S1 has a molecular weight of 1.3 × 106。
4. The preparation method according to claim 1, wherein in S1, the solid-to-liquid ratio of ammonium metatungstate to water is (0.5-0.6): 1 g/ml; the solid-liquid ratio of the polyvinylpyrrolidone to the water is (0.2-0.4): 1 g/ml.
5. The preparation method according to claim 1, wherein the calcination temperature in S3 is 500-650 ℃, the temperature rise rate is 1-5 ℃/min, and the temperature is maintained for 2-4 hours.
6. The method according to claim 1, wherein the dipping temperature in S4 is 80-90 ℃ and the dipping time is 0.5-3 hours.
7. The preparation method according to claim 1, wherein the calcination temperature in S4 is 600-700 ℃ and the calcination time is 1-3 h.
8. The copper-doped tungsten trioxide composite nanofiber material prepared by the preparation method as set forth in any one of claims 1 to 7.
9. The use of the copper-doped tungsten trioxide composite nanofiber material of claim 8 in water body pollution.
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