CN110327914A - A kind of tungstic acid/cadmium tungstate nanofiber catalysis material and the preparation method and application thereof - Google Patents
A kind of tungstic acid/cadmium tungstate nanofiber catalysis material and the preparation method and application thereof Download PDFInfo
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- CN110327914A CN110327914A CN201910763020.7A CN201910763020A CN110327914A CN 110327914 A CN110327914 A CN 110327914A CN 201910763020 A CN201910763020 A CN 201910763020A CN 110327914 A CN110327914 A CN 110327914A
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- tungstic acid
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- cadmium tungstate
- nanofiber
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- 239000000463 material Substances 0.000 title claims abstract description 137
- 238000006555 catalytic reaction Methods 0.000 title claims abstract description 110
- 239000002121 nanofiber Substances 0.000 title claims abstract description 96
- 238000002360 preparation method Methods 0.000 title claims abstract description 52
- 229910052793 cadmium Inorganic materials 0.000 title claims abstract description 50
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 title claims abstract description 45
- PBYZMCDFOULPGH-UHFFFAOYSA-N tungstate Chemical compound [O-][W]([O-])(=O)=O PBYZMCDFOULPGH-UHFFFAOYSA-N 0.000 title claims abstract description 45
- CMPGARWFYBADJI-UHFFFAOYSA-L tungstic acid Chemical compound O[W](O)(=O)=O CMPGARWFYBADJI-UHFFFAOYSA-L 0.000 title claims abstract description 40
- 239000002243 precursor Substances 0.000 claims abstract description 50
- 239000004098 Tetracycline Substances 0.000 claims abstract description 44
- 229960002180 tetracycline Drugs 0.000 claims abstract description 44
- 229930101283 tetracycline Natural products 0.000 claims abstract description 44
- 235000019364 tetracycline Nutrition 0.000 claims abstract description 44
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims abstract description 39
- 239000000835 fiber Substances 0.000 claims abstract description 32
- 150000003522 tetracyclines Chemical class 0.000 claims abstract description 32
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims abstract description 23
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims abstract description 23
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims abstract description 23
- 238000006731 degradation reaction Methods 0.000 claims abstract description 20
- 230000015556 catabolic process Effects 0.000 claims abstract description 19
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 15
- 229960000935 dehydrated alcohol Drugs 0.000 claims abstract description 15
- 239000012046 mixed solvent Substances 0.000 claims abstract description 14
- LHQLJMJLROMYRN-UHFFFAOYSA-L cadmium acetate Chemical compound [Cd+2].CC([O-])=O.CC([O-])=O LHQLJMJLROMYRN-UHFFFAOYSA-L 0.000 claims abstract description 13
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims abstract description 11
- 239000002131 composite material Substances 0.000 claims description 28
- 238000003756 stirring Methods 0.000 claims description 15
- 230000008859 change Effects 0.000 claims description 14
- 238000010041 electrostatic spinning Methods 0.000 claims description 11
- 239000000203 mixture Substances 0.000 claims description 8
- 229910052721 tungsten Inorganic materials 0.000 claims description 6
- 238000007254 oxidation reaction Methods 0.000 claims description 4
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 2
- 229910052760 oxygen Inorganic materials 0.000 claims description 2
- 239000001301 oxygen Substances 0.000 claims description 2
- 239000007921 spray Substances 0.000 claims description 2
- 239000010937 tungsten Substances 0.000 claims description 2
- 239000002071 nanotube Substances 0.000 claims 1
- 230000001699 photocatalysis Effects 0.000 abstract description 12
- 238000007146 photocatalysis Methods 0.000 abstract description 10
- 238000005516 engineering process Methods 0.000 abstract description 2
- 238000003837 high-temperature calcination Methods 0.000 abstract description 2
- 238000009987 spinning Methods 0.000 abstract description 2
- 239000011941 photocatalyst Substances 0.000 description 26
- 230000000052 comparative effect Effects 0.000 description 25
- 238000002835 absorbance Methods 0.000 description 20
- 238000006243 chemical reaction Methods 0.000 description 19
- 229910001220 stainless steel Inorganic materials 0.000 description 13
- 239000010935 stainless steel Substances 0.000 description 13
- 238000003917 TEM image Methods 0.000 description 12
- OFVLGDICTFRJMM-WESIUVDSSA-N tetracycline Chemical compound C1=CC=C2[C@](O)(C)[C@H]3C[C@H]4[C@H](N(C)C)C(O)=C(C(N)=O)C(=O)[C@@]4(O)C(O)=C3C(=O)C2=C1O OFVLGDICTFRJMM-WESIUVDSSA-N 0.000 description 12
- 238000010792 warming Methods 0.000 description 10
- 238000010438 heat treatment Methods 0.000 description 9
- 238000001878 scanning electron micrograph Methods 0.000 description 8
- 230000003197 catalytic effect Effects 0.000 description 7
- 238000000034 method Methods 0.000 description 7
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 6
- 229920003023 plastic Polymers 0.000 description 6
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- 239000003054 catalyst Substances 0.000 description 5
- 238000005286 illumination Methods 0.000 description 5
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- 238000004519 manufacturing process Methods 0.000 description 4
- 230000005540 biological transmission Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000001027 hydrothermal synthesis Methods 0.000 description 3
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Chemical compound [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 235000013339 cereals Nutrition 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000003292 glue Substances 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- -1 polyethylene Polymers 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 238000006479 redox reaction Methods 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- XMVONEAAOPAGAO-UHFFFAOYSA-N sodium tungstate Chemical compound [Na+].[Na+].[O-][W]([O-])(=O)=O XMVONEAAOPAGAO-UHFFFAOYSA-N 0.000 description 2
- 239000006228 supernatant Substances 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- 229910020350 Na2WO4 Inorganic materials 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 239000000908 ammonium hydroxide Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000003115 biocidal effect Effects 0.000 description 1
- 230000008033 biological extinction Effects 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 230000003760 hair shine Effects 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 1
- RXPAJWPEYBDXOG-UHFFFAOYSA-N hydron;methyl 4-methoxypyridine-2-carboxylate;chloride Chemical compound Cl.COC(=O)C1=CC(OC)=CC=N1 RXPAJWPEYBDXOG-UHFFFAOYSA-N 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000003760 magnetic stirring Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 239000002070 nanowire Substances 0.000 description 1
- 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 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 150000004040 pyrrolidinones Chemical class 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 238000000518 rheometry Methods 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000012876 topography Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 229910001930 tungsten oxide Inorganic materials 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
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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
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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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/40—Catalysts, in general, characterised by their form or physical properties characterised by dimensions, e.g. grain size
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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
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- B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
- B01J35/58—Fabrics or filaments
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- 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
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/38—Organic compounds containing nitrogen
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- 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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Abstract
The present invention relates to a kind of tungstic acid/cadmium tungstate nanofiber catalysis materials and the preparation method and application thereof.Ammonium metatungstate and cadmium acetate are dissolved in the in the mixed solvent being made of dehydrated alcohol and n,N-Dimethylformamide by the present invention, and polyvinylpyrrolidone is added and obtains spinnability precursor sol；By the rheological characteristic and spinning technology parameter that control spinnability precursor sol, prepare precursor fibre, then by precursor fibre high-temperature calcination at different temperatures, tungstic acid/cadmium tungstate nanofiber catalysis material is obtained, and preferred experimental program prepares the nanofiber catalysis material with tube-in-tube structure through the invention.Tungstic acid prepared by the present invention/cadmium tungstate nanofiber catalysis material realizes high efficiency photocatalysis degradation tetracycline under visible light, for degradation rate up to 93.1%, preparation method step is simple, low in cost in 120min, and can be recycled, significantly reduce application cost.
Description
Technical field
The present invention relates to a kind of tungstic acid/cadmium tungstate nanofiber catalysis materials and the preparation method and application thereof, belong to
In catalysis material technical field.
Background technique
With the continuous development of current social industrialized production, the dirts such as sewage, antibiotic for being generated in industrial processes
Dye object causes serious influence to people's lives and health.Therefore, improvement environment purification, which becomes, urgently solves
Certainly the problem of.In current environmental problem regulation, Photocatalitic Technique of Semiconductor has can be directly using solar energy as light source
The special performance of redox reaction is driven, is shown up prominently in terms of solving environmental problem.
Cadmium tungstate (CdWO4) have preferable chemistry, optics, structural behaviour and excellent heat steady in all tungstates
It is qualitative.Also, cadmium tungstate (CdWO4) be that a kind of earth resource is abundant, low-cost material, have good catalytic performance and
Electrochemical stability.However, CdWO4With wider band gap (3.8eV), the response range to solar spectrum, photoproduction are limited
The quick of carrier compound also limits its practical application.Therefore, a series of semiconductors are used to and CdWO4Compound building is heterogeneous
Knot is to improve its photocatalysis performance.For example, Colloids and Surfaces A:Physicochemical and
Engineering Aspects 522 (2017): 346-354, it was recently reported that the CdWO of hydro-thermal method combination immersion method preparation4/BiOI
Photochemical catalyst；Chinese patent literature CN105642316A (application number 201510975834.9), which is disclosed, a kind of prepares BiOI/
CdWO4The method of heterojunction photocatalyst, this method is using bismuth nitrate, sodium tungstate, potassium iodide and cadmium acetate as raw material, through two step water
BiOI/CdWO is prepared in thermal method4Heterojunction photocatalyst, the catalyst are the CdWO in nano bar-shape4Area load is irregular
Nano particle BiOI；CdWO prepared by the prior art4/ BiOI heterojunction structure photochemical catalyst compared with single photochemical catalyst,
Its photocatalysis effect improves；But the material scatter of preparation is poor, it is serious to reunite, which is unfavorable for photo-generated carrier
Transmission and separation, and prepared photochemical catalyst is more difficult recycles and reuses.
Summary of the invention
In view of the deficiencies of the prior art, the present invention provides a kind of tungstic acid/cadmium tungstate nanofiber catalysis materials
And the preparation method and application thereof, realize high efficiency photocatalysis degradation tetracycline under visible light, and tungstic acid/cadmium tungstate Nanowire
Catalysis material recoverable is tieed up, significantly reduces production cost, and tool has been prepared by preferred experimental program
There is the tube-in-tube nanostructure of special appearance.
Term explanation:
Room temperature: room temperature of the present invention has meaning well known in the art, generally refers to 20-25 DEG C.
Technical scheme is as follows:
A kind of tungstic acid/cadmium tungstate nanofiber catalysis material, which is characterized in that the catalysis material is by three
The composite nano-fiber material of tungsten oxide and cadmium tungstate composition.
Preferred according to the present invention, the composite nano fiber is one-dimensional linear structure, and diameter 100-600nm is long
Degree is 3-15 μm.
Preferred according to the present invention, the composite nano fiber is to include in the pipe of nanometer die and hollow Nano outer tube
Pipe structure, length are 10-15 μm, and the diameter of the nanometer die and hollow Nano outer tube is respectively 100-200nm and 400-
500nm。
Preferred according to the present invention, the tungstic acid/cadmium tungstate nanofiber catalysis material is by ammonium metatungstate, second
Sour cadmium and polyvinylpyrrolidone are that reaction raw materials prepare spinnability precursor sol, are made after electrostatic spinning and calcining.
It is further preferred that the molar ratio of Cd and W is 1:(1-3 in the spinnability precursor sol).
A kind of preparation method of tungstic acid/cadmium tungstate nanofiber catalysis material, comprises the following steps that
(1) preparation of spinnability precursor sol
Ammonium metatungstate and cadmium acetate are dissolved in the in the mixed solvent being made of dehydrated alcohol and n,N-Dimethylformamide,
It is 0.1-1.0PaS that polyvinylpyrrolidone (PVP), which is added, to viscosity, stirs evenly, obtains spinnability precursor sol；
(2) tungstic acid/cadmium tungstate precursor fibre preparation
The spinnability precursor sol that step (1) is obtained is 15-35 DEG C, voltage 10-30kV in temperature, sprays rate
To carry out electrostatic spinning under conditions of 0.1-1.5mL/h, precursor fibre is obtained；
(3) tungstic acid/cadmium tungstate nanofiber catalysis material preparation
By precursor fibre made from step (2), the dry 12-36h under the conditions of 40-100 DEG C, with the speed of 1-5 DEG C/min
Rate is warming up to 400-600 DEG C, keeps the temperature 60-180min to get tungstic acid/cadmium tungstate nanofiber catalysis material.
Preferred according to the present invention, the molar ratio of Cd and W is 1:(1- in spinnability precursor sol described in step (1)
3)；It is further preferred that the molar ratio of Cd and W is 1:(1.25-2 in the spinnability precursor sol).
It is preferred according to the present invention, in the mixed solvent dehydrated alcohol described in step (1) and n,N-Dimethylformamide
Volume ratio is 1:(0.5-2)；It is further preferred that the volume of the in the mixed solvent dehydrated alcohol and n,N-Dimethylformamide
Than for 1:(1-2).
Preferred according to the present invention, the molal volume ratio of cadmium acetate described in step (1) and mixed solvent is 1:(8-
15), unit mol/L.
Preferred according to the present invention, the weight average molecular weight of polyvinylpyrrolidone described in step (1) is 40,000-300 ten thousand；
It is further preferred that the weight average molecular weight of the polyvinylpyrrolidone is 1,000,000-150 ten thousand；Most preferably, the polyethylene
The weight average molecular weight 1,300,000 of pyrrolidones, available optimal nanofiber catalysis material.
Preferred according to the present invention, the reception distance of electrostatic spinning described in step (2) is 20-35cm；Spraying rate is
1.5mL/h, voltage 20-30kV, temperature are 20-25 DEG C.
It is preferred according to the present invention, the dry 12-24h under the conditions of being 40-60 DEG C of dry condition described in step (3).
Preferred according to the present invention, heating is to be warming up to 500-600 DEG C with the rate of 1-3 DEG C/min described in step (3),
Keep the temperature 60-120min.
It is further preferred that heating described in step (3) is that 500 DEG C are warming up to the rate of 3 DEG C/min, heat preservation
120min.The tungstic acid being prepared under the Elevated Temperature Conditions-cadmium tungstate nanofiber catalysis material be include nanometer die
With the tube-in-tube structure of hollow Nano outer tube, length is 10-15 μm, the diameter difference of the nanometer die and hollow Nano outer tube
For 100-200nm and 400-500nm.
Ammonium metatungstate and cadmium acetate are dissolved in the mixing being made of dehydrated alcohol and N,N-dimethylformamide by the present invention
In solvent, polyvinylpyrrolidone is added and obtains spinnability precursor sol；By the rheology for controlling spinnability precursor sol
Property and spinning technology parameter, prepare precursor fibre and then by precursor fibre high-temperature calcination at different temperatures obtain three oxygen
Change tungsten/cadmium tungstate nanofiber catalysis material, and preferred experimental program is prepared with tube-in-tube structure through the invention
Nanofiber catalysis material.Tungstic acid prepared by the present invention/cadmium tungstate nanofiber catalysis material realizes visible
High efficiency photocatalysis degradation tetracycline under light, and can be recycled, further reduce cost.
Above-mentioned tungstic acid/cadmium tungstate nanofiber catalysis material is applied to the photocatalytic oxidation degradation of tetracycline.
Beneficial effects of the present invention are as follows:
1, for catalysis material, microscopic appearance is one of the key factor for influencing its photocatalysis performance.The present invention
The tungstic acid of one-dimensional linear structure/cadmium tungstate nanofiber catalysis material, the nanometer of especially preferred tube-in-tube structure
Fiber catalysis material is conducive to the transmission and transfer and the transmission of photo-generated carrier and separation of electronics, to guarantee more
Light induced electron and hole participate in redox reaction, greatly enhance photocatalysis efficiency, under visible light illumination, photocatalytic-oxidation
Change tetracycline, degradation rate is up to 93.1% in 120min.
2, tungstic acid produced by the present invention/cadmium tungstate nanofiber catalysis material diameter dimension is relatively uniform, overcomes
Hydro-thermal method is easy to the shortcomings that reuniting；WO3With CdWO4Make material that more visible lights can be absorbed after compound, is conducive to improve light
Catalytic efficiency.
3, preparation method step of the invention is simple, easily operated, low in cost；And the material of one-dimensional linear pattern is just
It is recycled in by sedimentation, can be recycled, further reduce cost.
Detailed description of the invention
Fig. 1 is WO made from embodiment 13/CdWO4X-ray diffraction (XRD) spectrogram of nanofiber catalysis material；
Fig. 2 is WO made from embodiment 13/CdWO4The SEM image of nanofiber catalysis material；In figure, a WO3/
CdWO4The SEM image of nanofiber catalysis material low magnification, b are the SEM image of high-amplification-factor；
Fig. 3 is WO made from embodiment 13/CdWO4The TEM image of nanofiber catalysis material；In figure, a WO3/
CdWO4The TEM image of nanofiber catalysis material low magnification, b are the TEM image of high-amplification-factor；
Fig. 4 is WO made from embodiment 23/CdWO4The TEM image of nanofiber catalysis material；In figure, a WO3/
CdWO4The TEM image of nanofiber catalysis material low magnification, b are the TEM image of high-amplification-factor；
Fig. 5 is WO made from embodiment 33/CdWO4The TEM image of nanofiber catalysis material；In figure, a WO3/
CdWO4The TEM image of nanofiber catalysis material low magnification, b are the TEM image of high-amplification-factor；
Fig. 6 is WO made from comparative example 23/CdWO4The SEM image of composite photocatalyst material；In figure, a WO3/CdWO4It is multiple
The SEM image of light combination catalysis material low magnification, b are the SEM image of high-amplification-factor；
Fig. 7 is WO made from embodiment 13/CdWO4Nanofiber catalysis material light under the irradiation of simulated solar radiant
The absorbance curve of catalytic degradation tetracycline；Curve is corresponding in turn to 0-120min described in figure from top to bottom in figure；
Fig. 8 is WO made from embodiment 23/CdWO4Nanofiber catalysis material light under the irradiation of simulated solar radiant
The absorbance curve of catalytic degradation tetracycline；Curve is corresponding in turn to 0-120min described in figure from top to bottom in figure；
Fig. 9 is WO made from comparative example 13/CdWO4Composite photocatalyst material photocatalysis under the irradiation of simulated solar radiant
The absorbance curve of degradation tetracycline；Curve is corresponding in turn to 0-120min described in figure from top to bottom in figure；
Figure 10 is WO made from comparative example 23/CdWO4Composite photocatalyst material photocatalysis under the irradiation of simulated solar radiant
The absorbance curve of degradation tetracycline；Curve is corresponding in turn to 0-120min described in figure from top to bottom in figure；
Figure 11 is WO made from embodiment 13/CdWO4The C/ of tetracycline after the catalysis reaction of nanofiber catalysis material
C0With the change curve of light application time；In figure, a is the C/C of 60min dark reaction0Change curve, b are the C/ under illumination condition
C0Change curve；
Figure 12 is WO made from embodiment 23/CdWO4The C/ of tetracycline after the catalysis reaction of nanofiber catalysis material
C0With the change curve of light application time；In figure, a is the C/C of 60min dark reaction0Change curve, b are the C/ under illumination condition
C0Change curve；
Figure 13 is WO made from comparative example 13/CdWO4The C/C of tetracycline after composite photocatalyst material catalysis reaction0With
The change curve of light application time；In figure, a is the C/C of 60min dark reaction0Change curve, b are the C/C under illumination condition0Become
Change curve graph；
Figure 14 is WO made from comparative example 23/CdWO4The C/C of tetracycline after composite photocatalyst material catalysis reaction0With
The change curve of light application time；In figure, a is the C/C of 60min dark reaction0Change curve, b are the C/C under illumination condition0Become
Change curve graph；
Figure 15 is WO made from embodiment 13/CdWO4Nanofiber catalysis material weight under the irradiation of simulated solar radiant
Four degradation efficiency histograms to tetracycline are recycled again；
Figure 16 is WO made from comparative example 13/CdWO4Composite photocatalyst material repeats to follow under the irradiation of simulated solar radiant
Ring utilizes four degradation efficiency histograms to tetracycline.
Specific embodiment
The present invention is described further combined with specific embodiments below, but protection scope of the present invention is not limited to
This.Experimental method described in following embodiments is unless otherwise specified conventional method simultaneously；The reagent and material, such as nothing
Specified otherwise commercially obtains；Device therefor is conventional equipment.Wherein: polyvinylpyrrolidone is polyethylene
Pyrrolidones K90, weight average molecular weight are 1,300,000.
Embodiment 1
A kind of tungstic acid/cadmium tungstate (WO3/CdWO4) nanofiber catalysis material preparation method, including step is such as
Under:
(1) preparation of spinnability precursor sol: by 0.3079g (W:1.25mmol) ammonium metatungstate and 0.2665g (Cd:
1mmol) cadmium acetate is dissolved in the in the mixed solvent of 5mL dehydrated alcohol and 5mL n,N-Dimethylformamide composition, stirs to complete
Fully dissolved is added 1g polyvinylpyrrolidone (PVP), stirs evenly, and it is molten to obtain the spinnability presoma that viscosity is 0.5PaS
Glue；
(2)WO3/CdWO4The preparation of precursor fibre: with the plastic injector with stainless steel syringe needle by spinnability presoma
Colloidal sol is sprayed onto receiver board, and the reception distance between the stainless steel syringe needle and receiver board of syringe is 20cm, spinnability presoma
The ejection rate of colloidal sol be 1.5mL/h, voltage 20kV, electrostatic spinning temperature control at 25 DEG C, obtain precursor fibre；
(3)WO3/CdWO4The preparation of nanofiber catalysis material: precursor fibre made from step (2) is dry at 60 DEG C
Dry 12h, is subsequently placed in high temperature furnace in dry case, is warming up to 500 DEG C with the heating rate of 3 DEG C/min, keep the temperature 120min to get
WO3/CdWO4Nanofiber catalysis material.
Fig. 1 is the WO that the present embodiment is prepared3/CdWO4The X-ray diffraction (XRD) of nanofiber catalysis material is composed
Figure；
Fig. 2 is the WO that the present embodiment is prepared3/CdWO4The SEM image of nanofiber catalysis material；Fig. 3 is this reality
Apply the WO that example is prepared3/CdWO4The TEM image of nanofiber catalysis material；As shown in Figure 1, after 500 DEG C of sintering,
WO3/CdWO4The diffraction maximum and monocline CdWO of nanofiber catalysis material4(JCPDS No.14-0676) and monocline WO3
(JCPDS No.71-2141) can be corresponded to well；As shown in Figure 2, tungstic acid/cadmium tungstate that the present embodiment is prepared
Nanofiber catalysis material be include the tube-in-tube structure of nanometer die and hollow Nano outer tube, and diameter is relatively uniform, long
Degree is 10-15 μm, and the diameter of nanometer die and hollow Nano outer tube is respectively 100-200nm and 400-500nm；Fig. 3 is into one
Step proves the pattern of prepared WO3/CdWO4 nanofiber catalysis material, and being includes nanometer die and hollow Nano outer tube
Tube-in-tube structure.
Embodiment 2
A kind of tungstic acid/cadmium tungstate (WO3/CdWO4) nanofiber catalysis material preparation method, including step is such as
Under:
(1) preparation of spinnability precursor sol: by 0.3695g (W:1.5mmol) ammonium metatungstate and 0.2665g (Cd:
1mmol) cadmium acetate is dissolved in the in the mixed solvent of 5mL dehydrated alcohol and 7mL n,N-Dimethylformamide composition, stirs to complete
Fully dissolved is added 1g polyvinylpyrrolidone (PVP), stirs evenly, and it is molten to obtain the spinnability presoma that viscosity is 0.5PaS
Glue；
(2)WO3/CdWO4The preparation of precursor fibre: with the plastic injector with stainless steel syringe needle by spinnability presoma
Colloidal sol is sprayed onto receiver board, and the reception distance between the stainless steel syringe needle and receiver board of syringe is 25cm, spinnability presoma
The ejection rate of colloidal sol be 1.5mL/h, voltage 20kV, electrostatic spinning temperature control at 25 DEG C, obtain precursor fibre；
(3)WO3/CdWO4The preparation of nanofiber catalysis material: precursor fibre made from step (2) is dry at 60 DEG C
Dry 12h, is subsequently placed in high temperature furnace in dry case, is warming up to 550 DEG C with the heating rate of 1 DEG C/min, keep the temperature 120min to get
WO3/CdWO4Nanofiber catalysis material.
Fig. 4 is WO made from the present embodiment3/CdWO4The TEM image of nanofiber catalysis material.As shown in Figure 4, this reality
Apply the WO that example is prepared3/CdWO4The diameter of nanofiber catalysis material is 400-500nm, and diameter is relatively uniform, length
It is 10-15 μm, is one-dimensional linear pattern.
Embodiment 3
A kind of tungstic acid/cadmium tungstate (WO3/CdWO4) nanofiber catalysis material preparation method, including step is such as
Under:
(1) preparation of spinnability precursor sol: by 0.4927g (W:2mmol) ammonium metatungstate and 0.2665g (Cd:
1mmol) cadmium acetate is dissolved in the in the mixed solvent of 5mL dehydrated alcohol and 9mL n,N-Dimethylformamide composition, stirs to complete
Fully dissolved is added 1.2g polyvinylpyrrolidone (PVP), stirs evenly, and obtains the spinnability presoma that viscosity is 0.7PaS
Colloidal sol；
(2)WO3/CdWO4The preparation of precursor fibre: with the plastic injector with stainless steel syringe needle by spinnability presoma
Colloidal sol is sprayed onto receiver board, and the reception distance between the stainless steel syringe needle and receiver board of syringe is 25cm, spinnability presoma
The ejection rate of colloidal sol be 1.5mL/h, voltage 25kV, electrostatic spinning temperature control at 25 DEG C, obtain precursor fibre；
(3)WO3/CdWO4The preparation of nanofiber catalysis material: precursor fibre made from step (2) is dry at 40 DEG C
It is dry in dry case to be subsequently placed in high temperature furnace for 24 hours, be warming up to 550 DEG C with the heating rate of 1 DEG C/min, keep the temperature 120min to get
WO3/CdWO4Nanofiber catalysis material.
Fig. 5 is WO made from the present embodiment3/CdWO4The TEM image of nanofiber catalysis material.As shown in Figure 5, this reality
Apply the WO that example is prepared3/CdWO4The diameter of nanofiber catalysis material is 300-500nm, and it is one-dimensional that length, which is 3-8 μm,
Linear presence, and have bulky grain on fiber.
Embodiment 4
A kind of tungstic acid/cadmium tungstate (WO3/CdWO4) nanofiber catalysis material preparation method, including step is such as
Under:
(1) preparation of spinnability precursor sol: by 0.6159g (W:2.5mmol) ammonium metatungstate and 0.2665g (Cd:
1mmol) cadmium acetate is dissolved in the in the mixed solvent of 5mL dehydrated alcohol and 10mL n,N-Dimethylformamide composition, stirs to complete
Fully dissolved is added 1.2g polyvinylpyrrolidone (PVP), stirs evenly, and obtains the spinnability presoma that viscosity is 0.8PaS
Colloidal sol；
(2)WO3/CdWO4The preparation of precursor fibre: with the plastic injector with stainless steel syringe needle by spinnability presoma
Colloidal sol is sprayed onto receiver board, and the reception distance between the stainless steel syringe needle and receiver board of syringe is 20cm, spinnability presoma
The ejection rate of colloidal sol be 1.5mL/h, voltage 25kV, electrostatic spinning temperature control at 25 DEG C, obtain precursor fibre；
(3)WO3/CdWO4The preparation of nanofiber catalysis material: precursor fibre made from step (2) is dry at 40 DEG C
It is dry in dry case to be subsequently placed in high temperature furnace for 24 hours, be warming up to 600 DEG C with the heating rate of 2 DEG C/min, keep the temperature 60min to get
WO3/CdWO4Nanofiber catalysis material.
Embodiment 5
A kind of tungstic acid/cadmium tungstate (WO3/CdWO4) nanofiber catalysis material preparation method, including step is such as
Under:
(1) preparation of spinnability precursor sol: by 0.7390g (W:3mmol) ammonium metatungstate and 0.2665g (Cd:
1mmol) cadmium acetate is dissolved in the in the mixed solvent of 5mL dehydrated alcohol and 10mL n,N-Dimethylformamide composition, stirs to complete
Fully dissolved is added 1g polyvinylpyrrolidone (PVP), stirs evenly, and obtains the spinnability precursor sol that viscosity is 1PaS；
(2)WO3/CdWO4The preparation of precursor fibre: with the plastic injector with stainless steel syringe needle by spinnability presoma
Colloidal sol is sprayed onto receiver board, and the reception distance between the stainless steel syringe needle and receiver board of syringe is 30cm, spinnability presoma
The ejection rate of colloidal sol be 1.5mL/h, voltage 30kV, electrostatic spinning temperature control at 20 DEG C, obtain precursor fibre；
(3)WO3/CdWO4The preparation of nanofiber catalysis material: precursor fibre made from step (2) is dry at 60 DEG C
Dry 12h, is subsequently placed in high temperature furnace in dry case, is warming up to 600 DEG C with the heating rate of 2 DEG C/min, keep the temperature 120min to get
WO3/CdWO4Nanofiber catalysis material.
Comparative example 1
A kind of tungstic acid/cadmium tungstate (WO3/CdWO4) composite photocatalyst material preparation method, which is normal
Hydro-thermal method is advised, is comprised the following steps that
(1)CdWO4The preparation of nanometer rods
By 5mmol Na2WO4·2H2O and 5mmol Cd (NO3)2·4H2O is dissolved in 15mL deionized water and stirs
30min, in whipping process, it is 9.30 that ammonium hydroxide to solution ph, which is added dropwise,；Obtained transparent white solution is put into stainless steel height
It presses in kettle, is heated for 24 hours under 180 DEG C of high temperature；It is washed repeatedly with dehydrated alcohol and deionized water, obtains white powder；
(2) WO has been synthesized using CVD method3Laminated structure
It takes 0.5g tungsten powder to be put into alumina crucible and is put into Muffle furnace, be warming up to 600 with the heating rate of 10 DEG C/min
DEG C, 3h is calcined at 600 DEG C；Then it cools down at room temperature, collects yellow powder；
(3)WO3/CdWO4The preparation of composite photocatalyst material
Yellow powder made from white powder made from step (1) and step (2) is respectively placed according to mass ratio 1:1 and is contained
In the glass beaker of 10mL dehydrated alcohol, ultrasonic disperse 1h；Dispersion liquid after dispersion is mixed to and carried out magnetic stirring 1h, is then existed
12h is heated under 80 DEG C of high temperature；Gained powder calcines 2h under 550 DEG C of high temperature, obtains WO3/CdWO4Composite photocatalyst material.
Comparative example 2
A kind of tungstic acid/cadmium tungstate (WO3/CdWO4) composite photocatalyst material preparation method, comprise the following steps that
(1) preparation of spinnability precursor sol: by 0.9854g (W:4mmol) ammonium metatungstate and 0.2665g (Cd:
1mmol) cadmium acetate is dissolved in the in the mixed solvent of 5mL dehydrated alcohol and 5mL n,N-Dimethylformamide composition, stirs to complete
Fully dissolved is added 1.5g polyvinylpyrrolidone (PVP), stirs evenly, and obtains the spinnability presoma that viscosity is 0.7PaS
Colloidal sol；
(2)WO3/CdWO4The preparation of precursor fibre: with the plastic injector with stainless steel syringe needle by spinnability presoma
Colloidal sol is sprayed onto receiver board, and the reception distance between the stainless steel syringe needle and receiver board of syringe is 25cm, spinnability presoma
The ejection rate of colloidal sol be 1.5mL/h, voltage 25kV, electrostatic spinning temperature control at 25 DEG C, obtain precursor fibre；
(3)WO3/CdWO4The preparation of nanofiber catalysis material: precursor fibre made from step (2) is dry at 40 DEG C
It is dry in dry case to be subsequently placed in high temperature furnace for 24 hours, be warming up to 500 DEG C with the heating rate of 1 DEG C/min, keep the temperature 60min to get
WO3/CdWO4Composite photocatalyst material.
Fig. 6 is the WO that this comparative example is prepared3/CdWO4The SEM image of composite photocatalyst material, this is right as shown in Figure 6
The WO that ratio is prepared3/CdWO4Composite photocatalyst material is that broken tubulose is mingled with bulky grain, with embodiment 1, embodiment
The nanofiber catalysis material of 2 preparations is compared, and the sample topography of this comparative example preparation is inhomogenous and tubulose is broken serious.
Application examples 1
The photocatalytic degradation of tetracycline
By WO made from embodiment 1 and embodiment 23/CdWO4Nanofiber catalysis material and comparative example 1, comparative example 2
WO obtained3/CdWO4Composite photocatalyst material is applied to the photocatalytic degradation of tetracycline (TC), and light source used is the xenon of 500W
Lamp, simulated solar radiant, the concentration of tetracycline (TC) solution are 50mg/L, the specific steps are as follows:
Firstly, at room temperature, 0.06g catalysis material being added in tetracycline (TC) solution of 50mL, is then put in
Magnetic agitation 60min is in camera bellows to reach absorption-desorption balance, during which, takes out 4mL solution every 10min；Then, mould is opened
Quasi- light source, takes 4mL solution every 20min；The solution taken out every time centrifuge separation is taken into supernatant liquor, respectively with UV-2550 points
Light photometer test supernatant at top (370nm) absorbance；And catalysis material is recycled.
Fig. 7 is that the WO3/CdWO4 nanofiber catalysis material of tube-in-tube structure made from embodiment 1 shines in analog light source
The absorbance curve of lower photocatalytic degradation tetracycline (TC) is penetrated, Fig. 8 is the WO of one-dimensional linear structure made from embodiment 23/CdWO4
The absorbance curve of nanofiber catalysis material photocatalytic degradation tetracycline (TC) under analog light source irradiation, Fig. 9 are comparison
WO made from example 13/CdWO4Composite photocatalyst material extinction of photocatalytic degradation tetracycline (TC) under analog light source irradiation is write music
Line, Figure 10 are WO made from comparative example 23/CdWO4Composite photocatalyst material photocatalytic degradation tetracycline under analog light source irradiation
(TC) absorbance curve, Detection wavelength are 300-500nm.It can be seen from the figure that the absorbance peak of tetracycline
At 370nm, the WO of embodiment 1 and embodiment 23/CdWO4Nanofiber catalysis material is catalyzed reaction under analog light source
After 120min, absorbance value of the tetracycline at 370nm is below the composite photocatalyst material of comparative example 1 and comparative example 2
Material, illustrates the WO of one-dimensional linear structure prepared by the present invention especially tube-in-tube structure3/CdWO4Nanofiber catalysis material light
Catalytic efficiency significantly improves, the WO of tube-in-tube structure3/CdWO4Degradation effect of the nanofiber catalysis material to tetracycline (TC)
It is more excellent.
Suction of the WO3/CdWO4 nanofiber catalysis material of tube-in-tube structure made from embodiment 1 in dark reaction 60min
As shown in fig. 11a, the WO3/CdWO4 nanofiber catalysis material of one-dimensional linear structure prepared by embodiment 2 exists luminosity curve
As figure 12 a shows, WO3/CdWO4 composite photocatalyst material prepared by comparative example 1 is dark anti-for the absorbance curve of dark reaction 60min
Answer the absorbance curve of 60min as depicted in fig. 13 a, WO3/CdWO4 composite photocatalyst material prepared by comparative example 2 is in dark reaction
As shown in figures 14a, the purpose of dark reaction is the influence for excluding catalysis material and adsorbing to the absorbance curve of 60min, the results show that
WO prepared by cloudy, turbid phase, embodiment 1 and embodiment 23/CdWO4Nanofiber catalysis material and comparative example 1, comparative example 2
The WO of preparation3/CdWO4After dark reaction carries out 10 minutes, the absorbance of tetracycline does not have substantially composite photocatalyst material
It changes, catalysis material can't catalytic degradation tetracycline under the conditions of illustrating dark reaction；
The WO3/CdWO4 nanofiber catalysis material of tube-in-tube structure made from embodiment 1 is under different light application times
The absorbance change curve of reaction solution as shown in figure 11b, embodiment 2 prepare one-dimensional linear structure WO3/CdWO4 nanometer
As shown in Figure 12b, prepared by comparative example 1 for the absorbance change curve of fiber catalysis material reaction solution under different light application times
WO3/CdWO4 composite photocatalyst material reaction solution under different light application times absorbance change curve as illustrated in fig. 13b,
The absorbance change curve of WO3/CdWO4 composite photocatalyst material reaction solution under different light application times prepared by comparative example 2
As shown in fig. 14b, the WO for the tube-in-tube structure that comparing embodiment 1 is prepared3/CdWO4Nanofiber catalysis material and implementation
The WO of one-dimensional linear structure prepared by example 23/CdWO4It is prepared in nanofiber catalysis material and comparative example 1, comparative example 2
WO3/CdWO4Composite photocatalyst material, the WO of one-dimensional linear structure prepared by the present invention especially tube-in-tube structure3/CdWO4It receives
Rice fiber catalysis material photocatalysis efficiency is significantly higher, the WO of tube-in-tube structure3/CdWO4Nanofiber catalysis material is to four
The degradation effect of ring element (TC) is more excellent.
Catalysis material is calculated to the photocatalytic oxidation degradation efficiency of tetracycline (TC) according to public formula (I).
Public formula (I):
η=[(C0-Ct)/C0] × 100%,
In formula (I), C0For the absorbance that solution measures for the first time, CtThe absorbance measured for the t time.
The WO3/CdWO4 nanofiber catalysis material of tube-in-tube structure prepared by embodiment 1 is under analog light source irradiation
Repeated recycling utilize four times as shown in figure 15 to the degradation efficiency of tetracycline (TC), WO3/CdWO4 complex light prepared by comparative example 1
Catalysis material analog light source irradiation under repeated recycling utilize four times it is as shown in figure 16 to the degradation efficiency of tetracycline (TC), by scheming
It is found that after four times recycle, the light of the WO3/CdWO4 nanofiber catalysis material of tube-in-tube structure prepared by embodiment 1
Catalytic effect is still very high, up to 91.3%, and comparative example 1 prepare WO3/CdWO4 composite photocatalyst material four times circulation with
Afterwards, the degradation efficiency of sample reduces about 18%, only 46.3%, compared with sample prepared by embodiment 1, cycle performance and steady
It is qualitative all poor, illustrate WO prepared by the present invention3/CdWO4Nanofiber catalysis material is with good stability, Ke Yichong
It recycles again, greatly reduces production cost.
Claims (10)
1. a kind of tungstic acid/cadmium tungstate nanofiber catalysis material, which is characterized in that the catalysis material is by three oxygen
Change the composite nano-fiber material of tungsten and cadmium tungstate composition.
2. tungstic acid as described in claim 1/cadmium tungstate nanofiber catalysis material, which is characterized in that described answers
Conjunction nanofiber is one-dimensional linear structure, and diameter 100-600nm, length is 3-15 μm.
3. tungstic acid as described in claim 1/cadmium tungstate nanofiber catalysis material, which is characterized in that described answers
Closing nanofiber is the tube-in-tube structure for including nanometer die and hollow Nano outer tube, and length is 10-15 μm, the nanotube
The diameter of core and hollow Nano outer tube is respectively 100-200nm and 400-500nm.
4. a kind of tungstic acid/cadmium tungstate nanofiber catalysis material preparation method, which is characterized in that such as including step
Under:
(1) preparation of spinnability precursor sol
Ammonium metatungstate and cadmium acetate are dissolved in the in the mixed solvent being made of dehydrated alcohol and n,N-Dimethylformamide, are added
Polyvinylpyrrolidone (PVP) to viscosity is 0.1-1.0 PaS, stirs evenly, obtains spinnability precursor sol；
(2) tungstic acid/cadmium tungstate precursor fibre preparation
The spinnability precursor sol that step (1) is obtained is 15-35 DEG C, voltage 10-30kV in temperature, sprays rate and is
Electrostatic spinning is carried out under conditions of 0.1-1.5mL/h, obtains precursor fibre；
(3) tungstic acid/cadmium tungstate nanofiber catalysis material preparation
By precursor fibre made from step (2), the dry 12-36h under the conditions of 40-100 DEG C, with the rate liter of 1-5 DEG C/min
Temperature keeps the temperature 60-180min to 400-600 DEG C to get tungstic acid/cadmium tungstate nanofiber catalysis material.
5. a kind of preparation method of tungstic acid/cadmium tungstate nanofiber catalysis material as claimed in claim 4, feature
It is, the molar ratio of Cd and W is 1:(1-3 in spinnability precursor sol described in step (1)).
6. a kind of preparation method of tungstic acid/cadmium tungstate nanofiber catalysis material as claimed in claim 4, feature
It is, the volume ratio of in the mixed solvent dehydrated alcohol described in step (1) and n,N-Dimethylformamide is 1:(0.5-2).
7. a kind of preparation method of tungstic acid/cadmium tungstate nanofiber catalysis material as claimed in claim 4, feature
It is, the molal volume ratio of cadmium acetate described in step (1) and mixed solvent is 1:(8-15), unit mol/L.
8. a kind of preparation method of tungstic acid/cadmium tungstate nanofiber catalysis material as claimed in claim 4, feature
It is, the weight average molecular weight of polyvinylpyrrolidone described in step (1) is 40,000-300 ten thousand.
9. a kind of preparation method of tungstic acid/cadmium tungstate nanofiber catalysis material as claimed in claim 4, feature
It is, the reception distance of electrostatic spinning described in step (2) is 20-35cm；Ejection rate is 1.5mL/h, voltage 20-
30kV, temperature are 20-25 DEG C.
10. the photocatalytic-oxidation that tungstic acid described in claim 1/cadmium tungstate nanofiber catalysis material is applied to tetracycline
Change degradation.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111185219A (en) * | 2020-03-19 | 2020-05-22 | 东北大学秦皇岛分校 | Preparation method of bismuth vanadate/graphite phase carbon nitride nano-fiber |
| CN111282580A (en) * | 2020-03-23 | 2020-06-16 | 齐鲁工业大学 | Silver-modified cobalt tungstate/cadmium tungstate nanofiber photocatalytic material and preparation method and application thereof |
| CN115634686A (en) * | 2022-09-09 | 2023-01-24 | 齐鲁工业大学 | Photocatalytic material MWO capable of responding to visible light, near infrared light and selective degradation thereof 4 And preparation method and application thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106466599A (en) * | 2016-08-30 | 2017-03-01 | 华南师范大学 | A kind of preparation method of the tungsten trioxide nano fiber of nucleocapsid structure |
| CN107837807A (en) * | 2017-11-01 | 2018-03-27 | 浙江海洋大学 | A kind of WO3/Bi2MoO6Composite photocatalyst material and preparation method thereof |
| CN109999792A (en) * | 2019-04-17 | 2019-07-12 | 齐鲁工业大学 | A kind of porous ZnWO4/WO3Nano pipe light catalyst and simple controllable preparation method |
-
2019
- 2019-08-19 CN CN201910763020.7A patent/CN110327914B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106466599A (en) * | 2016-08-30 | 2017-03-01 | 华南师范大学 | A kind of preparation method of the tungsten trioxide nano fiber of nucleocapsid structure |
| CN107837807A (en) * | 2017-11-01 | 2018-03-27 | 浙江海洋大学 | A kind of WO3/Bi2MoO6Composite photocatalyst material and preparation method thereof |
| CN109999792A (en) * | 2019-04-17 | 2019-07-12 | 齐鲁工业大学 | A kind of porous ZnWO4/WO3Nano pipe light catalyst and simple controllable preparation method |
Non-Patent Citations (1)
| Title |
|---|
| IMRAN ASLAM ET AL.: "A novel Z-scheme WO3/CdWO4 photocatalyst with enhanced visible-light photocatalytic activity for the degradation of organic pollutants", 《RSC ADVANCES》 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111185219A (en) * | 2020-03-19 | 2020-05-22 | 东北大学秦皇岛分校 | Preparation method of bismuth vanadate/graphite phase carbon nitride nano-fiber |
| CN111282580A (en) * | 2020-03-23 | 2020-06-16 | 齐鲁工业大学 | Silver-modified cobalt tungstate/cadmium tungstate nanofiber photocatalytic material and preparation method and application thereof |
| CN115634686A (en) * | 2022-09-09 | 2023-01-24 | 齐鲁工业大学 | Photocatalytic material MWO capable of responding to visible light, near infrared light and selective degradation thereof 4 And preparation method and application thereof |
| CN115634686B (en) * | 2022-09-09 | 2024-04-16 | 齐鲁工业大学 | Photocatalytic material MWO capable of responding to visible light and near infrared light and selectively degrading 4 Preparation method and application thereof |
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