CN104475163A - Polyvinylidene fluoride film for visible light catalysis and preparation method of polyvinylidene fluoride film - Google Patents
Polyvinylidene fluoride film for visible light catalysis and preparation method of polyvinylidene fluoride film Download PDFInfo
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Abstract
The invention relates to a polyvinylidene fluoride film for visible light catalysis. A ZnS/CuS nanometer composite semiconductor material with a visible light catalysis property is added to the polyvinylidene fluoride film. A preparation method of the polyvinylidene fluoride film comprises the following steps: firstly preparing the ZnS/CuS nanometer composite semiconductor material by taking a monodispersed ZnS solid microsphere prepared by adopting a hydrothermal synthesis method as a precursor and a copper-containing water solution as a copper source; and then mixing a ZnS/CuS composite hollow sphere, polyvinylidene fluoride, an additive and a plasticizer with a solvent to obtain a film forming solution, defoaming, scraping a film, shaping and solidifying to prepare a target object. The PVDF (Polyvinylidene Fluoride) film prepared by adopting the method has the characteristics of high strength, good toughness, good acid-alkali corrosion resistance, organic solvent resistance, radiation resistance and heat resistance, and the like; in addition, PVDF can be used for easily forming the film, has the good pore structure, and can be used for greatly enlarging the specific area of a catalyst, and thus the relatively high catalytic activity is achieved.
Description
Technical field
The present invention relates to the technical field of visible light catalytic, is specifically related to a kind of polyvinylidene fluoride film for visible light catalytic and preparation method thereof.
Background technology
The conventional nano powder catalyst such as titanium dioxide, zinc oxide, zirconia has good photocatalysis performance with it and is subject to the favor of people in the aqueous solution and meteoropathic reaction.But in aqueous, pulverous nanocatalyst is easy to reunite, and the activity of catalyst is reduced greatly; Powder catalyst not easily precipitates, and the recovery and reuse of catalyst are restricted.Therefore, solving one of effective way of the recycling of catalyst is be cured by catalyst.The solidification of catalyst not only can solve a recovery difficult problem for catalyst, and can solve the difficult problem that catalyst is easy to reunion.Thus the stability of catalyst can be improved, solve catalyst and be easy to a poisoning difficult problem.
TiO
2be carried on the substrates such as glass, silicon chip, cellulose membrane, polyether sulfone, Kynoar and had a large amount of reports at nearly 10 years.In Long-Time Service, polytetrafluoroethylene (PTFE) (Nafion) film has the attack and enough stability that stop hydroxyl radical free radical, but uses its price too expensive as the substrate of catalyst, causes it not use on a large scale.
Kynoar (PVDF) intensity is high, good toughness, and has good acid-alkali-corrosive-resisting, radiation hardness, heat-resisting, good film-forming property, has the features such as good pore structure.Pvdf membrane uses as the substrate of ZnS/CuS nanometer, composite semiconductor material, can increase substantially the specific area of catalyst, thus show higher catalytic activity.
Summary of the invention
The object of the invention is for above-mentioned existing problems, provide a kind of polyvinylidene fluoride film for visible light catalytic and preparation method thereof, this polyvinylidene fluoride film can increase substantially the specific area of catalyst, thus shows higher catalytic activity; Its preparation technology is simple, easy to implement.
Technical scheme of the present invention:
A kind of polyvinylidene fluoride film for visible light catalytic, add the ZnS/CuS nanometer, composite semiconductor material with visible light catalytic performance in polyvinylidene fluoride film, the mass ratio of polyvinylidene fluoride film and ZnS/CuS nanometer, composite semiconductor material is 15-24:0.1-2.
A described preparation method for the polyvinylidene fluoride film of visible light catalytic, step is as follows:
(1) preparation of ZnS/CuS nanometer, composite semiconductor material
1) will be Zn source containing the aqueous solution of zinc ion, the aqueous solution of sulfur-containing anion is S source, Zn source, S source are dissolved in the mixed solvent be made up of deionized water and surfactant respectively, obtain S source solution and Zn source solution, under fast stirring, sulphur source solution is slowly joined in the solution of zinc source, move into after stirring in reactor, 100 DEG C of insulation 10h, after sample is cooled to room temperature, by white precipitate product separation, products therefrom deionized water and absolute ethyl alcohol are alternately washed 3-8 time, after centrifugal, drying, obtain monodispersed ZnS solid microsphere;
2) sputtering ZnS solid microsphere and Cu source are disperseed in deionized water respectively, obtain the ZnS aqueous solution and the Cu source aqueous solution, under magnetic stirring Cu source is joined in the aqueous solution of ZnS microballoon, be stirred to mixed solution and become field gray suspension, then suspension is joined 100 DEG C of insulation 0.5h-2h in reactor, by alternately washing 3-8 time of the black product deionized water that obtains and absolute ethyl alcohol, after centrifugal, drying, obtain the nano combined hollow ball of ZnS/CuS;
(2) for the preparation of the polyvinylidene fluoride film of visible light catalytic
1) above-mentioned obtained ZnS/CuS composite hollow ball, Kynoar, additive, plasticizer are mixed with solvent, 50-95 DEG C is stirred to and mixes, and obtains preparation liquid;
2) by above-mentioned preparation liquid deaeration 24-48 hour under vacuum is 0.075-0.095MPa, temperature 60-80 DEG C condition, then adopt the tape casting knifing, then be immersed in coagulating bath and shape and solidify, obtain object.
Described Zn source is ZnSO
4, ZnCl
2, zinc acetate, ZnCO
4with the mixture of one or more arbitrary proportions in zinc lactate; S source is the mixture of one or more arbitrary proportions in sodium thiosulfate, thioacetic acid amine, ammonium sulfide and thiocarbamide; Surfactant is the mixture of one or more arbitrary proportions in polyethylene glycol, paraffin and stearic acid; The volume ratio of deionized water and surfactant is 1-10:2-5; Zn source and the S source molar concentration in mixed solvent is 0.1-0.5mol/L; The mol ratio in Zn source and S source is 1-2:1-5.
Described Cu source is the mixture of one or more arbitrary proportions in copper citrate, copper sulphate and copper chloride; The mass ratio of ZnS solid microsphere and deionized water is 1-3:800-1500; The mass ratio of Cu source and deionized water is 4-8:1000-2000; Cu source and ZnS mass ratio be 1-4:1-2.
Described additive is the mixture of polyvinylpyrrolidone, one or more arbitrary proportions in polymethyl methacrylate, polyvinyl chloride, polyethylene glycol, lithium chloride, lithium perchlorate, glycerine and ethylene glycol; Plasticizer is one in epoxidized soybean oil and epoxyfatty acid or any two kinds; Solvent is the mixture of one or more arbitrary proportions in dimethylacetylamide, dimethyl formamide, acetone, dimethyl sulfoxide (DMSO), triethyl phosphate, trimethyl phosphate; The mass ratio of Kynoar, ZnS/CuS composite hollow ball, additive, plasticizer and solvent is 15-24:0.1-2:0-8:0-3:76-85.
It is 0.1-0.3mm that described the tape casting scrapes film thickness, and knifing speed is 1500-2500mm/h.
Described coagulating bath composition is the mixture of one or both solution arbitrary proportions in water and ethanol.
Advantage of the present invention is: the preparation method of this polyvinylidene fluoride film, and compared with the semi-conducting material of the ultraviolet light response such as titanium dioxide, zinc sulphide, ZnS/CuS nanometer, composite semiconductor material becomes visible light-responded new type structure of hud catalyst; ZnS/CuS nanometer, composite semiconductor material is joined in pvdf membrane the recovery difficult problem being cured and not only can solving catalyst, and the difficult problem that catalyst is easy to reunion can be solved; Obtained pvdf membrane intensity is high, good toughness, and there is good acid-alkali-corrosive-resisting, organic solvent-resistant, radiation hardness, the feature such as heat-resisting, PVDF is easy to film forming and has good pore structure, can increase substantially the specific area of catalyst, thus shows higher catalytic activity; This polyvinylidene fluoride film is used for organic degraded in the degraded of visible light catalytic industrial wastewater and air.
Detailed description of the invention
embodiment 1:
For a polyvinylidene fluoride film for visible light catalytic, add the ZnS/CuS nanometer, composite semiconductor material with visible light catalytic performance in polyvinylidene fluoride film, the mass ratio of polyvinylidene fluoride film and ZnS/CuS nanometer, composite semiconductor material is 18:1.
The preparation method of the described polyvinylidene fluoride film for visible light catalytic, step is as follows:
(1) preparation of ZnS/CuS nanometer, composite semiconductor material
1) by zinc acetate, sodium thiosulfate is dissolved in the mixed solvent be made up of deionized water and surfactant respectively, obtain Zn source solution and S source solution, the volume ratio of deionized water and surfactant is 10:4, Zn source and the S source molar concentration in mixed solvent is 0.214mol/L, under fast stirring, sulphur source solution is slowly joined in the solution of zinc source, the mol ratio in Zn source and S source is 1:1, move into after stirring in reactor, 100 DEG C of insulation 10h, after sample is cooled to room temperature, by white precipitate product separation, products therefrom deionized water and absolute ethyl alcohol are replaced washing 5 times, centrifugal, after drying, obtain monodispersed ZnS solid microsphere,
2) by sputtering ZnS solid microsphere and CuCl
2disperse in deionized water respectively, obtain the ZnS aqueous solution and the Cu source aqueous solution, the mass ratio of ZnS solid microsphere and deionized water is 1:428; The mass ratio of Cu source and deionized water is 6:1000, under magnetic stirring Cu source is joined in the aqueous solution of ZnS microballoon, Cu source and ZnS mass ratio be 175:306, be stirred to mixed solution and become field gray suspension, then suspension is joined 100 DEG C of insulation 1h in reactor, the black product deionized water obtained and absolute ethyl alcohol are replaced washing 5 times, after centrifugal, drying, obtains ZnS/CuS nanometer, composite semiconductor material; Detection shows: the obtained efficiency of ZnS/CuS nanometer, composite semiconductor material to catalytic degradation rhodamine B solution is 98%;
(2) for the preparation of the polyvinylidene fluoride film of visible light catalytic
1) by above-mentioned obtained ZnS/CuS nanometer, composite semiconductor material, Kynoar, dimethylacetylamide mixing, the mass ratio of Kynoar, ZnS/CuS nanometer, composite semiconductor material, dimethylacetylamide is 18:1:81,60 DEG C are stirred to and mix, and obtain preparation liquid;
2) by the deaeration 24 hours under vacuum is 0.085MPa, temperature 60 C condition of above-mentioned preparation liquid, then in flat membrane casting equipment, the tape casting knifing is carried out, scraping film thickness is 0.2mm, knifing speed is 1800mm/h, be immersed in again in coagulating bath and shape and solidify, coagulating bath composition is water-bath, obtained object.
Detection shows: the polyvinylidene fluoride film that this embodiment obtains is when rhodamine B concentration is 20mg/l, be 50% to the efficiency of catalytic degradation rhodamine B solution, the maximum pull of film is 7.13 Ns, tensile strength 2.41MPa, elongation at break is 43.81%, and because ZnS/CuS nanometer, composite semiconductor material is doped in polyvinylidene fluoride film, film entirety being used for can by photocatalysis, directly take out from waste liquid with the film crossed, and the photocatalysis efficiency of the film reclaimed remains unchanged.
embodiment 2:
For a polyvinylidene fluoride film for visible light catalytic, add the ZnS/CuS nanometer, composite semiconductor material with visible light catalytic performance in polyvinylidene fluoride film, the mass ratio of polyvinylidene fluoride film and ZnS/CuS nanometer, composite semiconductor material is 18:1.
The preparation method of the described polyvinylidene fluoride film for visible light catalytic, step is as follows:
(1) preparation of ZnS/CuS nanometer, composite semiconductor material is with embodiment 1;
(2) for the preparation of the polyvinylidene fluoride film of visible light catalytic
1) by above-mentioned obtained ZnS/CuS nanometer, composite semiconductor material, Kynoar, dimethylacetylamide mixing, the mass ratio of Kynoar, ZnS/CuS nanometer, composite semiconductor material, polyvinylpyrrolidone and polymethyl methacrylate (1:1), epoxidized soybean oil, dimethylacetylamide is 18:1:3:3:75,60 DEG C are stirred to and mix, and obtain preparation liquid;
2) with embodiment 1.
Detection shows: the polyvinylidene fluoride film that this embodiment obtains is when rhodamine B concentration is 20mg/l, and be 45% to the efficiency of catalytic degradation rhodamine B solution, the maximum pull of film is 7.79 Ns, tensile strength 2.60MPa, and elongation at break is 77.41%.
embodiment 3:
For a polyvinylidene fluoride film for visible light catalytic, add the ZnS/CuS nanometer, composite semiconductor material with visible light catalytic performance in polyvinylidene fluoride film, the mass ratio of polyvinylidene fluoride film and ZnS/CuS nanometer, composite semiconductor material is 18:0.5.
The preparation method of the described polyvinylidene fluoride film for visible light catalytic, step is as follows:
(1) preparation of ZnS/CuS nanometer, composite semiconductor material is with embodiment 1
(2) for the preparation of the polyvinylidene fluoride film of visible light catalytic
1) by above-mentioned obtained ZnS/CuS nanometer, composite semiconductor material, Kynoar, dimethylacetylamide mixing, the mass ratio of Kynoar, ZnS/CuS nanometer, composite semiconductor material, dimethylacetylamide is 18:0.5:81.5,60 DEG C are stirred to and mix, and obtain preparation liquid;
2) with embodiment 1.
Detection shows: the polyvinylidene fluoride film that this embodiment obtains is when rhodamine B concentration is 20mg/l, and be 24% to the efficiency of catalytic degradation rhodamine B solution, the maximum pull of film is 8.07 Ns, tensile strength 2.69MPa, and elongation at break is 101.36%.
embodiment 4:
For a polyvinylidene fluoride film for visible light catalytic, add the ZnS/CuS nanometer, composite semiconductor material with visible light catalytic performance in polyvinylidene fluoride film, the mass ratio of polyvinylidene fluoride film and ZnS/CuS nanometer, composite semiconductor material is 18:2.
The preparation method of the described polyvinylidene fluoride film for visible light catalytic, step is as follows:
(1) preparation of ZnS/CuS nanometer, composite semiconductor material is with embodiment 1
(2) for the preparation of the polyvinylidene fluoride film of visible light catalytic
1) by above-mentioned obtained ZnS/CuS nanometer, composite semiconductor material, Kynoar, dimethylacetylamide mixing, the mass ratio of Kynoar, ZnS/CuS nanometer, composite semiconductor material, dimethylacetylamide is 18:2:80,60 DEG C are stirred to and mix, and obtain preparation liquid;
2) with embodiment 1.
Detection shows: the polyvinylidene fluoride film that this embodiment obtains is when rhodamine B concentration is 20mg/l, and be 60% to the efficiency of catalytic degradation rhodamine B solution, the maximum pull of film is 6.84 Ns, tensile strength 2.28MPa, and elongation at break is 22.86%.
As can be seen from the above embodiments, all embodiments have the combination property exceeding modern technologies, as can be seen from embodiment 1: obtained ZnS/CuS nanometer, composite semiconductor material is when rhodamine B concentration is 20mg/l, the efficiency of rhodamine B degradation is 98%, but the recovery of ZnS/CuS nanometer, composite semiconductor material is difficult, be unfavorable for reusing, and although obtained polyvinylidene fluoride film is on the low side for visible light photocatalytic degradation efficiency, but can recycle, thus solve a ZnS/CuS nanometer, composite semiconductor material recovery difficulty difficult problem for embodiment 1.
Finally it should be noted that, what above embodiment illustrated is technical scheme of the present invention, does not limit in any form real protection scope of the present invention.Although describe the present invention in detail in conjunction with optimum embodiment; but any technical staff should be understood that the protection domain of this patent; in the aim and scope of the technical program, do any pro forma change or be equal to substituting, all should belong to the prescription scope of this patent.
Claims (7)
1. the polyvinylidene fluoride film for visible light catalytic, it is characterized in that: add the ZnS/CuS nanometer, composite semiconductor material with visible light catalytic performance in polyvinylidene fluoride film, the mass ratio of polyvinylidene fluoride film and ZnS/CuS nanometer, composite semiconductor material is 15-24:0.1-2.
2., as claimed in claim 1 for a preparation method for the polyvinylidene fluoride film of visible light catalytic, it is characterized in that step is as follows:
(1) preparation of ZnS/CuS nanometer, composite semiconductor material
1) will be Zn source containing the aqueous solution of zinc ion, the aqueous solution of sulfur-containing anion is S source, Zn source, S source are dissolved in the mixed solvent be made up of deionized water and surfactant respectively, obtain S source solution and Zn source solution, under fast stirring, sulphur source solution is slowly joined in the solution of zinc source, move into after stirring in reactor, 100 DEG C of insulation 10h, after sample is cooled to room temperature, by white precipitate product separation, products therefrom deionized water and absolute ethyl alcohol are alternately washed 3-8 time, after centrifugal, drying, obtain monodispersed ZnS solid microsphere;
2) sputtering ZnS solid microsphere and Cu source are disperseed in deionized water respectively, obtain the ZnS aqueous solution and the Cu source aqueous solution, under magnetic stirring Cu source is joined in the aqueous solution of ZnS microballoon, be stirred to mixed solution and become field gray suspension, then suspension is joined 100 DEG C of insulation 0.5h-2h in reactor, by alternately washing 3-8 time of the black product deionized water that obtains and absolute ethyl alcohol, after centrifugal, drying, obtain the nano combined hollow ball of ZnS/CuS;
(2) for the preparation of the polyvinylidene fluoride film of visible light catalytic
1) above-mentioned obtained ZnS/CuS composite hollow ball, Kynoar, additive, plasticizer are mixed with solvent, 50-95 DEG C is stirred to and mixes, and obtains preparation liquid;
2) by above-mentioned preparation liquid deaeration 24-48 hour under vacuum is 0.075-0.095MPa, temperature 60-80 DEG C condition, then adopt the tape casting knifing, then be immersed in coagulating bath and shape and solidify, obtain object.
3. according to claim 2 for the preparation method of the polyvinylidene fluoride film of visible light catalytic, it is characterized in that: described Zn source is ZnSO
4, ZnCl
2, zinc acetate, ZnCO
4with the mixture of one or more arbitrary proportions in zinc lactate; S source is the mixture of one or more arbitrary proportions in sodium thiosulfate, thioacetic acid amine, ammonium sulfide and thiocarbamide; Surfactant is the mixture of one or more arbitrary proportions in polyethylene glycol, paraffin and stearic acid; The volume ratio of deionized water and surfactant is 1-10:2-5; Zn source and the S source molar concentration in mixed solvent is 0.1-0.5mol/L; The mol ratio in Zn source and S source is 1-2:1-5.
4. according to claim 2 for the preparation method of the polyvinylidene fluoride film of visible light catalytic, it is characterized in that: described Cu source is the mixture of one or more arbitrary proportions in copper citrate, copper sulphate and copper chloride; The mass ratio of ZnS solid microsphere and deionized water is 1-3:800-1500; The mass ratio of Cu source and deionized water is 4-8:1000-2000; Cu source and ZnS mass ratio be 1-4:1-2.
5. according to claim 2 for the preparation method of the polyvinylidene fluoride film of visible light catalytic, it is characterized in that: described additive is the mixture of polyvinylpyrrolidone, one or more arbitrary proportions in polymethyl methacrylate, polyvinyl chloride, polyethylene glycol, lithium chloride, lithium perchlorate, glycerine and ethylene glycol; Plasticizer is one in epoxidized soybean oil and epoxyfatty acid or any two kinds; Solvent is the mixture of one or more arbitrary proportions in dimethylacetylamide, dimethyl formamide, acetone, dimethyl sulfoxide (DMSO), triethyl phosphate, trimethyl phosphate; The mass ratio of Kynoar, ZnS/CuS composite hollow ball, additive, plasticizer and solvent is 15-24:0.1-2:0-8:0-3:76-85.
6. according to claim 2 for the preparation method of the polyvinylidene fluoride film of visible light catalytic, it is characterized in that: it is 0.1-0.3mm that described the tape casting scrapes film thickness, knifing speed is 1500-2500mm/h.
7. according to claim 2 for the preparation method of the polyvinylidene fluoride film of visible light catalytic, it is characterized in that: described coagulating bath composition is the mixture of one or both solution arbitrary proportions in water and ethanol.
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| CN114471627A (en) * | 2022-02-16 | 2022-05-13 | 武汉理工大学 | Antimony iodide and sulfide nanowire composite film with polyvinylidene fluoride as substrate, and preparation method and application thereof |
| CN114527179A (en) * | 2021-12-31 | 2022-05-24 | 西安理工大学 | Multi-element composite sulfide nano powder with flower-shaped core-shell structure and preparation method thereof |
| CN115057986A (en) * | 2022-07-01 | 2022-09-16 | 尼伦化学(上海)有限公司 | Photochromic TPU composition for military camouflage and preparation method thereof |
| CN115212886A (en) * | 2022-07-19 | 2022-10-21 | 吕梁学院 | Preparation method and application of film containing CoS/CoO microspheres |
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| CN114471627A (en) * | 2022-02-16 | 2022-05-13 | 武汉理工大学 | Antimony iodide and sulfide nanowire composite film with polyvinylidene fluoride as substrate, and preparation method and application thereof |
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| CN115212886A (en) * | 2022-07-19 | 2022-10-21 | 吕梁学院 | Preparation method and application of film containing CoS/CoO microspheres |
| CN115212886B (en) * | 2022-07-19 | 2023-10-13 | 吕梁学院 | Preparation method and application of CoS/CoO microsphere-containing film |
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Application publication date: 20150401 |