CN113680220B - Nanometer boron carbide/polyvinylidene fluoride film with photocatalysis effect and preparation method thereof - Google Patents
Nanometer boron carbide/polyvinylidene fluoride film with photocatalysis effect and preparation method thereof Download PDFInfo
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- 229910052580 B4C Inorganic materials 0.000 title claims abstract description 76
- INAHAJYZKVIDIZ-UHFFFAOYSA-N boron carbide Chemical compound B12B3B4C32B41 INAHAJYZKVIDIZ-UHFFFAOYSA-N 0.000 title claims abstract description 70
- 239000002033 PVDF binder Substances 0.000 title claims abstract description 69
- 229920002981 polyvinylidene fluoride Polymers 0.000 title claims abstract description 69
- 230000001699 photocatalysis Effects 0.000 title claims abstract description 42
- 238000007146 photocatalysis Methods 0.000 title claims abstract description 19
- 230000000694 effects Effects 0.000 title claims abstract description 18
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 239000000843 powder Substances 0.000 claims abstract description 29
- 238000005266 casting Methods 0.000 claims abstract description 13
- 239000003960 organic solvent Substances 0.000 claims abstract description 13
- 239000000463 material Substances 0.000 claims abstract description 9
- 238000000034 method Methods 0.000 claims abstract description 4
- 239000000243 solution Substances 0.000 claims description 37
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 32
- 239000002904 solvent Substances 0.000 claims description 26
- 239000007788 liquid Substances 0.000 claims description 25
- 239000002245 particle Substances 0.000 claims description 23
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical group CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 18
- 239000006185 dispersion Substances 0.000 claims description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- 238000001035 drying Methods 0.000 claims description 11
- 239000011259 mixed solution Substances 0.000 claims description 11
- 239000011248 coating agent Substances 0.000 claims description 10
- 238000000576 coating method Methods 0.000 claims description 10
- 238000007872 degassing Methods 0.000 claims description 10
- 229920000642 polymer Polymers 0.000 claims description 10
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 9
- 239000011521 glass Substances 0.000 claims description 8
- 238000000227 grinding Methods 0.000 claims description 8
- 239000012528 membrane Substances 0.000 claims description 8
- 239000000523 sample Substances 0.000 claims description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- 230000001112 coagulating effect Effects 0.000 claims description 2
- 230000015271 coagulation Effects 0.000 claims description 2
- 238000005345 coagulation Methods 0.000 claims description 2
- 238000005303 weighing Methods 0.000 claims description 2
- 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 abstract description 25
- 230000015556 catabolic process Effects 0.000 abstract description 3
- 239000002131 composite material Substances 0.000 abstract description 3
- 238000006731 degradation reaction Methods 0.000 abstract description 3
- 239000011159 matrix material Substances 0.000 abstract description 3
- 238000009303 advanced oxidation process reaction Methods 0.000 abstract description 2
- 238000004140 cleaning Methods 0.000 abstract description 2
- 238000011031 large-scale manufacturing process Methods 0.000 abstract description 2
- 238000000614 phase inversion technique Methods 0.000 abstract description 2
- 230000000704 physical effect Effects 0.000 abstract description 2
- 229920006254 polymer film Polymers 0.000 abstract description 2
- 238000001556 precipitation Methods 0.000 abstract description 2
- 229940043267 rhodamine b Drugs 0.000 description 23
- 239000011941 photocatalyst Substances 0.000 description 9
- 238000001782 photodegradation Methods 0.000 description 9
- 238000002835 absorbance Methods 0.000 description 7
- 238000004458 analytical method Methods 0.000 description 7
- 239000007864 aqueous solution Substances 0.000 description 7
- 239000003054 catalyst Substances 0.000 description 7
- 230000008859 change Effects 0.000 description 7
- 238000002336 sorption--desorption measurement Methods 0.000 description 7
- 229920000131 polyvinylidene Polymers 0.000 description 6
- 239000004065 semiconductor Substances 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 2
- 238000007605 air drying Methods 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000003344 environmental pollutant Substances 0.000 description 2
- 239000010842 industrial wastewater Substances 0.000 description 2
- 239000002957 persistent organic pollutant Substances 0.000 description 2
- 231100000719 pollutant Toxicity 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 238000003911 water pollution Methods 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 230000032900 absorption of visible light Effects 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 230000004298 light response Effects 0.000 description 1
- 238000013332 literature search Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 1
- 229920005597 polymer membrane Polymers 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0002—Organic membrane manufacture
- B01D67/0009—Organic membrane manufacture by phase separation, sol-gel transition, evaporation or solvent quenching
- B01D67/0011—Casting solutions therefor
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0002—Organic membrane manufacture
- B01D67/0009—Organic membrane manufacture by phase separation, sol-gel transition, evaporation or solvent quenching
- B01D67/0016—Coagulation
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/02—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor characterised by their properties
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/12—Composite membranes; Ultra-thin membranes
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
- B01D71/30—Polyalkenyl halides
- B01D71/32—Polyalkenyl halides containing fluorine atoms
- B01D71/34—Polyvinylidene fluoride
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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
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/18—Carbon
- B01J21/185—Carbon nanotubes
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- 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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- 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
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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
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
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- B01D2325/00—Details relating to properties of membranes
- B01D2325/10—Catalysts being present on the surface of the membrane or in the pores
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- 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
- C02F2101/308—Dyes; Colorants; Fluorescent agents
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- C02F2303/00—Specific treatment goals
- C02F2303/14—Maintenance of water treatment installations
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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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- C02F2305/10—Photocatalysts
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Abstract
The invention relates to a polyvinylidene fluoride film and a preparation method thereof, in particular to a nano boron carbide/polyvinylidene fluoride film with a photocatalysis effect and a preparation method thereof, belonging to the field of inorganic nano photocatalysis materials. The nanometer boron carbide/polyvinylidene fluoride film with the photocatalysis effect comprises the following components: 15-18wt% of polyvinylidene fluoride, 1-4wt% of nano boron carbide and 78-84wt% of organic solvent; comprising the following steps: 1) Pretreating materials; 2) Preparing a casting solution; 3) And (3) preparing the nano boron carbide/polyvinylidene fluoride film. The invention has the advantages that: the invention adopts the method that nanometer boron carbide powder is doped into a polymer film matrix, and a composite film material with photocatalysis effect is prepared by a submerged precipitation phase inversion method. The preparation process is simple and can be used for large-scale production. The prepared nano boron carbide/polyvinylidene fluoride photocatalytic film has good degradation effect on rhodamine solution with the concentration of 50 mg/L. The invention plays a role of self-cleaning through the advanced oxidation process and can be reused; the excellent physical properties increase the useful life of the film.
Description
Technical Field
The invention relates to a polyvinylidene fluoride film and a preparation method thereof, in particular to a nano boron carbide/polyvinylidene fluoride film with a photocatalysis effect and a preparation method thereof, belonging to the field of inorganic nano photocatalysis materials.
Background
Water pollution is one of the major environmental problems facing the world today, and industrial wastewater is rapidly increasing with the development of industry. Dye wastewater from textile and paper industry is a common and important water pollution problem, which seriously threatens the environment and human health. The photocatalytic technology is an emerging technology in recent years, and the target pollutants are mineralized by utilizing electron-hole pairs with strong redox capability generated after the photocatalyst semiconductor absorbs visible light. The process has no other pollutant, and is an effective means for degrading organic pollutant in water.
Nanometer boron carbide (B) 4 C) As a p-type semiconductor material, the material has relatively good band gap and strong visible light response capability. And boron carbide has a structure of an icosahedron with self-induced distortion and 3c-2e electron-deficient chemical bonds, so that a new intermediate energy gap state can be generated, the absorption of visible light is improved by reducing the conduction band edge of the boron carbide, and the service life of a photoexcited carrier of the boron carbide is longer than that of a traditional semiconductor (such as diamond-like carbon and a-Se). Boron carbide is therefore considered one of the most promising, lowest cost, and least toxic photocatalysts under visible light irradiation. However, the traditional photocatalyst powder is often dispersed in polluted water body in practical application, is not easy to recycle, is easy to cause secondary pollution of the water body, and is easy to agglomerate in the water body, so that the photocatalytic area is greatly reduced, and the photocatalytic activity is reduced.
How to solve the problem of recovery of nano photocatalyst powder, reducing agglomeration and increasing catalytic reaction area and improving photocatalytic activity of the nano photocatalyst powder is a key for enabling the nano photocatalyst powder to be widely applied to actual industrial wastewater treatment. The literature searches to find that there is no preparation method of the related nanometer boron carbide/polymer photocatalysis film.
Disclosure of Invention
The invention provides a nanometer boron carbide/polyvinylidene fluoride membrane with a photocatalysis effect and a preparation method thereof, and aims to prepare a nanometer boron carbide polymer composite membrane by doping nanometer boron carbide powder into a polymer membrane matrix, so as to solve the problems of degradation of organic pollutants in sewage and recovery of photocatalyst powder.
The invention has the photocatalysis effect nano boron carbide/polyvinylidene fluoride film for achieving the purpose, and consists of the following components: 15-18wt% of polyvinylidene fluoride, 1-4wt% of nano boron carbide and 78-84wt% of organic solvent.
The organic solvent is N, N-Dimethylacetamide (DMAC) or N, N-Dimethylformamide (DMF).
The preparation method of the nano boron carbide/polyvinylidene fluoride film with the photocatalytic effect is characterized by comprising the following steps of:
1) Material pretreatment, namely weighing 15-18wt% of polyvinylidene fluoride and 1-4wt% of nano boron carbide powder, and putting the powder into a blast drying oven for drying;
2) Preparing a casting solution: grinding the dried nano boron carbide powder to uniformly refine particles, then adding the particles into a half of organic solvent, performing ultrasonic dispersion by using a probe ultrasonic disperser to obtain dispersion liquid, and adding the dried polyvinylidene fluoride and the rest of organic solvent into the dispersion liquid to obtain mixed liquid; stirring the prepared mixed solution to completely dissolve the polyvinylidene fluoride in the organic solvent; carrying out ultrasonic degassing treatment on the stirred polymer solution to completely remove bubbles to obtain a coating solution;
3) Preparation of a nano boron carbide/polyvinylidene fluoride film: the coating solution was cast onto a clean glass plate, and the boron carbide/polyvinylidene fluoride film was immediately immersed in a coagulation bath using a film casting machine, and sufficiently immersed at room temperature to avoid solvent residue.
The grain diameter of the nanometer boron carbide is 30-50nm.
The polyvinylidene fluoride is 6010 or kf850.
The drying condition in the step 1) is that the drying is carried out for 2-4 hours at the temperature of 60-80 ℃.
The ultrasonic dispersion time in the step 2) is 15-30min.
The organic solvent is N, N-Dimethylacetamide (DMAC) or N, N-Dimethylformamide (DMF).
The stirring condition of the casting film liquid is that stirring is carried out for 12-15 hours at 40-60 ℃, and the time between ultrasonic degassing is 2-4 hours.
The coagulating bath is water or water and ethanol mixed solution.
The invention has the advantages that: the invention adopts the method that nanometer boron carbide powder is doped into a polymer film matrix, and a composite film material with photocatalysis effect is prepared by a submerged precipitation phase inversion method. The preparation process is simple and can be used for large-scale production. The prepared nano boron carbide/polyvinylidene fluoride photocatalytic film has good degradation effect on rhodamine solution with the concentration of 50 mg/L. The invention plays a role of self-cleaning through the advanced oxidation process and can be reused; the excellent physical properties increase the useful life of the film.
Detailed Description
The present invention will be described in detail below.
Example 1
50 ml rhodamine B solution is added into a culture dish (100 ml), and the photocatalytic activity of the nano boron carbide powder photocatalyst is studied under the irradiation of an ultraviolet lamp. Dispersing the nano boron carbide powder in rhodamine B solution, and standing for 30min in a dark room to reach adsorption-desorption equilibrium. The photocatalytic activity analysis was performed by detecting the absorbance change of rhodamine B solution (λ=554 nm) exposed to ultraviolet light in the presence of a catalyst and at room temperature using an ultraviolet lamp as an irradiation source. The three photodegradation efficiencies for rhodamine B are shown in table 1, and the photodegradation efficiency (η) is calculated from the following formula:
wherein: c represents the absorption intensity after photodegradation, ci represents the initial absorption intensity of rhodamine B solution, and the catalysis time is 20min.
Example 2
16wt% polyvinylidene fluoride of the model (kf 850) and 1wt% nano boron carbide powder of the particle size of 50nm were weighed and put into a forced air drying oven to be dried at 80℃for 4 hours. Grinding the dried nano boron carbide powder to uniformly refine particles, then adding the particles into 41.5wt% of N, N-dimethylacetamide solvent, performing ultrasonic dispersion for 30min by using a probe ultrasonic disperser to obtain dispersion liquid, and adding the dried polyvinylidene fluoride and 41.5wt% of N, N-dimethylacetamide solvent into the dispersion liquid to obtain mixed liquid. Stirring the prepared mixed solution for 12 hours at 60 ℃ to ensure that the polyvinylidene fluoride is completely dissolved in the N, N-dimethylacetamide solvent. The stirred polymer solution was subjected to ultrasonic degassing treatment for 2 hours. The coating solution was cast onto a clean glass plate and cast using a casting machine.
And immediately immersing the boron carbide/polyvinylidene fluoride film in water, and fully immersing the film at room temperature to avoid solvent residues, thus obtaining the nano boron carbide/polyvinylidene fluoride film. A50 ml (50 mg/L) rhodamine B solution was added to a petri dish (100 ml), and the photocatalytic activity of the polyvinylidene fluoride-boron carbide film was studied under ultraviolet light irradiation. The film of aqueous solution was allowed to stand in a dark room for 30min to reach adsorption-desorption equilibrium, and photocatalytic activity analysis was performed by detecting absorbance change of rhodamine B aqueous solution (λ=554 nm) exposed to ultraviolet light in the presence of a catalyst and at room temperature using an ultraviolet lamp as a light source. The three photodegradation efficiencies for rhodamine B are shown in table 1.
Example 3
16wt% polyvinylidene fluoride of the model (kf 850) and 2.5wt% nano boron carbide powder of the particle size of 30nm were weighed and put into a forced air drying oven to be dried at 60℃for 2 hours. Grinding the dried nanometer boron carbide powder to uniformly refine particles, then adding the particles into 40.75wt% of N, N-dimethylformamide solvent, performing ultrasonic dispersion for 15min by using a probe ultrasonic disperser to obtain dispersion liquid, and adding the dried polyvinylidene fluoride and 40.75wt% of N, N-dimethylformamide solvent into the dispersion liquid to obtain mixed liquid. The prepared mixed solution is stirred for 15 hours at 40 ℃ to ensure that the polyvinylidene fluoride is completely dissolved in the N, N-dimethylformamide solvent. The stirred polymer solution was subjected to ultrasonic degassing treatment for 4 hours. The coating solution was cast onto a clean glass plate and cast using a casting machine. And immediately immersing the boron carbide/polyvinylidene fluoride membrane into a mixed solution of water and ethanol, and fully immersing the membrane at room temperature to avoid solvent residues, thus obtaining the nano boron carbide/polyvinylidene fluoride membrane.
A50 ml (50 mg/L) rhodamine B solution was added to a petri dish (100 ml), and the photocatalytic activity of the polyvinylidene fluoride-boron carbide film was studied under ultraviolet light irradiation. The film of the aqueous solution was allowed to stand in the dark for 30min to reach adsorption-desorption equilibrium, and photocatalytic activity analysis was performed by detecting a change in absorbance value of rhodamine B solution (λ=554 nm) exposed to ultraviolet light in the presence of a catalyst and at room temperature using an ultraviolet lamp as an irradiation source. The three photodegradation efficiencies for rhodamine B are shown in table 1.
Example 4
16wt% polyvinylidene fluoride of the model (6010) and 4wt% nano boron carbide powder of the particle size of 25nm were weighed and put into a blast drying oven to be dried at 70 ℃ for 3 hours. Grinding the dried nanometer boron carbide powder to uniformly refine particles, then adding the particles into 40wt% of N, N-dimethylformamide solvent, performing ultrasonic dispersion for 20min by using a probe ultrasonic disperser to obtain dispersion liquid, and adding the dried polyvinylidene fluoride and 40wt% of N, N-dimethylformamide solvent into the dispersion liquid to obtain mixed liquid. The prepared mixed solution is stirred for 13 hours at 50 ℃ to ensure that the polyvinylidene fluoride is completely dissolved in the N, N-dimethylformamide solvent. The stirred polymer solution was subjected to ultrasonic degassing treatment for 3 hours. The coating solution was cast onto a clean glass plate and cast using a casting machine. And immediately immersing the boron carbide/polyvinylidene fluoride film in water, and fully immersing the film at room temperature to avoid solvent residues, thus obtaining the nano boron carbide/polyvinylidene fluoride film.
A50 ml rhodamine B solution was added to a petri dish (100 ml), and the photocatalytic activity of the polyvinylidene fluoride-boron carbide film was studied under ultraviolet light irradiation. The film of the aqueous solution was allowed to stand in the dark for 30min to reach adsorption-desorption equilibrium, and photocatalytic activity analysis was performed by detecting absorbance change of rhodamine B solution (λ=554 nm) exposed to ultraviolet light in the presence of a catalyst and at room temperature using an ultraviolet lamp as an irradiation source. The three photodegradation efficiencies for rhodamine B are shown in table 1.
Example 5
15wt% polyvinylidene fluoride of the model (6010) and 1wt% nano boron carbide powder of the particle size of 35nm were weighed and put into a blast drying oven to be dried for 3 hours at 75 ℃. Grinding the dried nano boron carbide powder to uniformly refine particles, then adding the particles into an N, N-dimethylacetamide solvent (42 wt percent) and performing ultrasonic dispersion for 25min by using a probe ultrasonic disperser to obtain a dispersion liquid, and adding the dried polyvinylidene fluoride and the N, N-dimethylacetamide solvent (42 wt percent) into the dispersion liquid to obtain a mixed liquid. The prepared mixed solution is stirred for 14 hours at 55 ℃ to ensure that the polyvinylidene fluoride is completely dissolved in the N, N-dimethylacetamide solvent. The stirred polymer solution was subjected to ultrasonic degassing treatment for 4 hours. The coating solution was cast onto a clean glass plate and cast using a casting machine. And immediately immersing the boron carbide/polyvinylidene fluoride film in water, and fully immersing the film at room temperature to avoid solvent residues, thus obtaining the nano boron carbide/polyvinylidene fluoride film.
A50 ml rhodamine B solution was added to a petri dish (100 ml), and the photocatalytic activity of the polyvinylidene fluoride-boron carbide film was studied under ultraviolet light irradiation. The film of the aqueous solution was allowed to stand in the dark for 30min to reach adsorption-desorption equilibrium, and photocatalytic activity analysis was performed by detecting absorbance change of rhodamine B solution (λ=554 nm) exposed to ultraviolet light in the presence of a catalyst and at room temperature using an ultraviolet lamp as an irradiation source. The three photodegradation efficiencies for rhodamine B are shown in table 1.
Example 6
18wt% polyvinylidene fluoride of the model (6010) and 3wt% nano boron carbide powder of the particle size of 45nm were weighed and put into a blast drying oven to be dried at 80 ℃ for 4 hours. Grinding the dried nano boron carbide powder to uniformly refine particles, then adding the particles into an N, N-dimethylacetamide solvent (39.5 wt percent) and performing ultrasonic dispersion for 30min by using a probe ultrasonic disperser to obtain a dispersion liquid, and adding the dried polyvinylidene fluoride and the N, N-dimethylacetamide solvent (39.5 wt percent) into the dispersion liquid to obtain a mixed liquid. Stirring the prepared mixed solution for 12 hours at 60 ℃ to ensure that the polyvinylidene fluoride is completely dissolved in the N, N-dimethylacetamide solvent. The stirred polymer solution was subjected to ultrasonic degassing treatment for 2 hours. The coating solution was cast onto a clean glass plate and cast using a casting machine. And immediately immersing the boron carbide/polyvinylidene fluoride film in water, and fully immersing the film at room temperature to avoid solvent residues, thus obtaining the nano boron carbide/polyvinylidene fluoride film.
A50 ml rhodamine B solution was added to a petri dish (100 ml), and the photocatalytic activity of the polyvinylidene fluoride-boron carbide film was studied under ultraviolet light irradiation. The film of the aqueous solution was allowed to stand in the dark for 30min to reach adsorption-desorption equilibrium, and photocatalytic activity analysis was performed by detecting absorbance change of rhodamine B solution (λ=554 nm) exposed to ultraviolet light in the presence of a catalyst and at room temperature using an ultraviolet lamp as an irradiation source. The three photodegradation efficiencies for rhodamine B are shown in table 1.
Example 7
18wt% polyvinylidene fluoride of the model (6010) and 1wt% nano boron carbide powder of the particle size of 30nm were weighed and put into a blast drying oven to be dried at 60 ℃ for 4 hours. Grinding the dried nano boron carbide powder to uniformly refine particles, then adding the particles into an N, N-dimethylacetamide solvent (40.5 wt percent) and performing ultrasonic dispersion for 30min by using a probe ultrasonic disperser to obtain a dispersion liquid, and adding the dried polyvinylidene fluoride and the N, N-dimethylacetamide solvent (40.5 wt percent) into the dispersion liquid to obtain a mixed liquid. Stirring the prepared mixed solution for 15 hours at 60 ℃ to ensure that the polyvinylidene fluoride is completely dissolved in the N, N-dimethylacetamide solvent. The stirred polymer solution was subjected to ultrasonic degassing treatment for 4 hours. The coating solution was cast onto a clean glass plate and cast using a casting machine. And immediately immersing the boron carbide/polyvinylidene fluoride film in water, and fully immersing the film at room temperature to avoid solvent residues, thus obtaining the nano boron carbide/polyvinylidene fluoride film.
A50 ml rhodamine B solution was added to a petri dish (100 ml), and the photocatalytic activity of the polyvinylidene fluoride-boron carbide film was studied under ultraviolet light irradiation. Will contain
The film of the aqueous solution was allowed to stand in the dark for 30min to reach adsorption-desorption equilibrium, and photocatalytic activity analysis was performed by detecting the absorbance change of rhodamine B solution (λ=554 nm) exposed to ultraviolet light in the presence of a catalyst and at room temperature using an ultraviolet lamp as an irradiation source. The three photodegradation efficiencies for rhodamine B are shown in table 1.
TABLE 1 photocatalytic degradation Performance test results of nano boron carbide powder photocatalyst and RHB of the present invention
。
Claims (9)
1. The nanometer boron carbide/polyvinylidene fluoride film with the photocatalysis effect is characterized by comprising the following components: 15-18wt% of polyvinylidene fluoride, 1-4wt% of nano boron carbide and 78-84wt% of organic solvent;
comprising the following steps:
1) Material pretreatment, namely weighing 15-18wt% of polyvinylidene fluoride and 1-4wt% of nano boron carbide powder, and putting the powder into a blast drying oven for drying;
2) Preparing a casting solution: grinding the dried nano boron carbide powder to uniformly refine particles, then adding the particles into a half of organic solvent, performing ultrasonic dispersion by using a probe ultrasonic disperser to obtain dispersion liquid, and adding the dried polyvinylidene fluoride and the rest of organic solvent into the dispersion liquid to obtain mixed liquid; stirring the prepared mixed solution to completely dissolve the polyvinylidene fluoride in the organic solvent; carrying out ultrasonic degassing treatment on the stirred polymer solution to completely remove bubbles to obtain a coating solution;
3) Preparation of a nano boron carbide/polyvinylidene fluoride film: the coating solution was cast onto a clean glass plate, and the boron carbide/polyvinylidene fluoride film was immediately immersed in a coagulation bath using a film casting machine, and sufficiently immersed at room temperature to avoid solvent residue.
2. The nano boron carbide/polyvinylidene fluoride film with photocatalysis effect according to claim 1, wherein the organic solvent is N, N-dimethylacetamide or N, N-dimethylformamide.
3. The nano boron carbide/polyvinylidene fluoride film with photocatalysis effect according to claim 1, characterized in that the particle size of the nano boron carbide is 30-50nm.
4. The nano boron carbide/polyvinylidene fluoride membrane with photocatalysis effect according to claim 1, characterized in that the polyvinylidene fluoride model is PVDF (6010) or PVDF (kf 850).
5. The nano boron carbide/polyvinylidene fluoride film with photocatalysis effect according to claim 1, wherein the drying condition in the step 1) is 60-80 ℃ for 2-4h.
6. The nano boron carbide/polyvinylidene fluoride film with photocatalysis effect according to claim 1, wherein the ultrasonic dispersion time in the step 2) is 15-30min.
7. The nano boron carbide/polyvinylidene fluoride film with photocatalysis effect according to claim 1, wherein the organic solvent is N, N-dimethylacetamide or N, N-dimethylformamide.
8. The method for preparing the nano boron carbide/polyvinylidene fluoride membrane with the photocatalytic effect according to claim 1, wherein the stirring condition of the casting solution is 40-60 ℃ and stirring is carried out for 12-15h, and the ultrasonic degassing is carried out for 2-4h.
9. The nano boron carbide/polyvinylidene fluoride membrane with the photocatalytic effect according to claim 1, wherein the coagulating bath is water or a water and ethanol mixed solution.
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