CN112007523A - Polyvinylidene fluoride mixed matrix film and preparation method thereof - Google Patents
Polyvinylidene fluoride mixed matrix film and preparation method thereof Download PDFInfo
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- CN112007523A CN112007523A CN202010795752.7A CN202010795752A CN112007523A CN 112007523 A CN112007523 A CN 112007523A CN 202010795752 A CN202010795752 A CN 202010795752A CN 112007523 A CN112007523 A CN 112007523A
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- 239000002033 PVDF binder Substances 0.000 title claims abstract description 47
- 229920002981 polyvinylidene fluoride Polymers 0.000 title claims abstract description 47
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 239000011159 matrix material Substances 0.000 title claims abstract description 5
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 35
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims abstract description 31
- 238000005266 casting Methods 0.000 claims abstract description 24
- 239000012528 membrane Substances 0.000 claims abstract description 23
- 239000004941 mixed matrix membrane Substances 0.000 claims abstract description 23
- 239000002105 nanoparticle Substances 0.000 claims abstract description 18
- 238000000034 method Methods 0.000 claims abstract description 15
- 238000005191 phase separation Methods 0.000 claims abstract description 13
- 239000002904 solvent Substances 0.000 claims abstract description 6
- 238000004729 solvothermal method Methods 0.000 claims abstract description 5
- 239000000654 additive Substances 0.000 claims abstract description 3
- 239000000243 solution Substances 0.000 claims description 43
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 16
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 13
- 239000008367 deionised water Substances 0.000 claims description 13
- 229910021641 deionized water Inorganic materials 0.000 claims description 13
- 238000009210 therapy by ultrasound Methods 0.000 claims description 11
- 238000006243 chemical reaction Methods 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 8
- 239000007788 liquid Substances 0.000 claims description 7
- 239000011259 mixed solution Substances 0.000 claims description 7
- 238000002791 soaking Methods 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 6
- GPNNOCMCNFXRAO-UHFFFAOYSA-N 2-aminoterephthalic acid Chemical compound NC1=CC(C(O)=O)=CC=C1C(O)=O GPNNOCMCNFXRAO-UHFFFAOYSA-N 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 5
- DUNKXUFBGCUVQW-UHFFFAOYSA-J zirconium tetrachloride Chemical compound Cl[Zr](Cl)(Cl)Cl DUNKXUFBGCUVQW-UHFFFAOYSA-J 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 4
- 239000011248 coating agent Substances 0.000 claims description 3
- 238000000576 coating method Methods 0.000 claims description 3
- 239000002245 particle Substances 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 claims 1
- 238000007606 doctor blade method Methods 0.000 claims 1
- 230000001699 photocatalysis Effects 0.000 abstract description 8
- 230000003373 anti-fouling effect Effects 0.000 abstract description 5
- 238000007146 photocatalysis Methods 0.000 abstract description 5
- 238000012360 testing method Methods 0.000 description 8
- 239000011521 glass Substances 0.000 description 6
- 108010058846 Ovalbumin Proteins 0.000 description 5
- 230000004907 flux Effects 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 229940092253 ovalbumin Drugs 0.000 description 5
- 238000011084 recovery Methods 0.000 description 4
- 239000002131 composite material Substances 0.000 description 3
- 239000012621 metal-organic framework Substances 0.000 description 3
- 238000007790 scraping Methods 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005286 illumination Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 238000005215 recombination Methods 0.000 description 2
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- 230000004044 response Effects 0.000 description 2
- 230000003595 spectral effect Effects 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- KSPIHGBHKVISFI-UHFFFAOYSA-N Diphenylcarbazide Chemical compound C=1C=CC=CC=1NNC(=O)NNC1=CC=CC=C1 KSPIHGBHKVISFI-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000010531 catalytic reduction reaction Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000004737 colorimetric analysis Methods 0.000 description 1
- 238000009295 crossflow filtration Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 235000019441 ethanol Nutrition 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000013110 organic ligand Substances 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- 239000002957 persistent organic pollutant Substances 0.000 description 1
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 1
- 238000006303 photolysis reaction Methods 0.000 description 1
- 230000015843 photosynthesis, light reaction Effects 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000003746 surface roughness Effects 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000000108 ultra-filtration Methods 0.000 description 1
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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
-
- 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
- B01D67/0079—Manufacture of membranes comprising organic and inorganic components
-
- 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
-
- 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
- B01D71/02—Inorganic material
- B01D71/024—Oxides
-
- 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
-
- 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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/1691—Coordination polymers, e.g. metal-organic frameworks [MOF]
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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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/22—Organic complexes
- B01J31/2204—Organic complexes the ligands containing oxygen or sulfur as complexing atoms
- B01J31/2208—Oxygen, e.g. acetylacetonates
- B01J31/2226—Anionic ligands, i.e. the overall ligand carries at least one formal negative charge
- B01J31/2243—At least one oxygen and one nitrogen atom present as complexing atoms in an at least bidentate or bridging ligand
-
- 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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
- B01J31/38—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 of titanium, zirconium or hafnium
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- B01J35/39—Photocatalytic properties
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- B01J35/40—Catalysts, in general, characterised by their form or physical properties characterised by dimensions, e.g. grain size
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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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- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
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- C02F2101/22—Chromium or chromium compounds, e.g. chromates
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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Abstract
The invention relates to a polyvinylidene fluoride mixed matrix film and a preparation method thereof, wherein the method comprises the following steps: preparing the TiO obtained by a solvothermal method2@UiO‑66‑NH2The nano particles and PVP are added into PVDF as additives to prepare TiO2@UiO‑66‑NH2The PVDF membrane casting solution is prepared into a polyvinylidene fluoride mixed matrix membrane by adopting a non-solvent induced phase separation method. Compared with the prior art, the TiO synthesized by the invention2@UiO‑66‑NH2the/PVDF mixed matrix membrane has higher anti-fouling and photocatalysis capacity of Cr (VI).
Description
Technical Field
The invention relates to the technical field of membrane separation, in particular to a polyvinylidene fluoride mixed matrix membrane and a preparation method thereof.
Background
TiO2The material has the characteristics of excellent physical and chemical properties, low cost, no toxicity and the like, and has wide application prospects in the fields of environmental protection (photocatalytic degradation of organic pollutants), clean energy (photolysis of water to produce hydrogen) and the like. However, the defects of rapid recombination of photo-generated electron-hole pairs, narrow spectral response range and the like limit TiO2As light three components, TiO is formed by design2And the composite structure of other materials can effectively improve and enhance the photocatalytic performance of the composite material.
Disclosure of Invention
The invention aims to overcome the defects in the prior art and provide a polyvinylidene fluoride mixed matrix membrane with high photocatalytic efficiency and strong anti-fouling capability and a preparation method thereof.
The purpose of the invention can be realized by the following technical scheme:
the metal organic framework Materials (MOFs) are microporous crystal materials formed by coordination of metal ions and organic ligands, have the performance of both inorganic materials and organic materials, and have wide application space. Wherein the Zr-based MOF material (UiO-66-NH)2) With the lowest unoccupied and highest occupied orbitals being appropriate, with TiO2Can transfer electrons and holes and reduce TiO2The band gap width of the band-gap is increased, and the spectral response range is expanded. TiO 22、UiO-66-NH2And a certain theoretical basis is provided for jointly constructing a composite structure, and the synergistic effect of the two components can ensure that TiO is subjected to2More photogenerated electrons and holes are generated under illumination, and TiO can be promoted2The transfer of the photo-generated electrons inhibits the recombination of the photo-generated electron hole pairs, and better photocatalysis performance is obtained.
A preparation method of a polyvinylidene fluoride mixed matrix film comprises the following steps: preparing the TiO obtained by a solvothermal method2@UiO-66-NH2The nano particles and PVP are added into PVDF as additives to prepare TiO2@UiO-66-NH2The PVDF membrane casting solution is prepared into a polyvinylidene fluoride mixed matrix membrane by adopting a non-solvent induced phase separation method (NIPS).
Further, the method comprises the steps of:
(1) according to the mass ratio, the TiO prepared by the solvothermal method2@UiO-66-NH2Dissolving the nano particles and PVDF in DMF to obtain a membrane casting solution;
(2) heating and stirring the casting solution, and standing for defoaming;
(3) coating the defoamed casting solution on a plate to form a film;
(4) immersing the plate with the membrane in a gel bath for phase separation;
(5) and soaking the membrane after phase separation in deionized water to obtain the polyvinylidene fluoride mixed matrix membrane.
Further, the TiO is2@UiO-66-NH2The mass ratio of PVP to PVDF is 1 (0.1-1) to 17.
Further, the TiO is2The @ UiO-66-NH nano-particles are prepared by the following steps:
(1-1) mixing TiO2The particles are added to DMF and, after stirring, TiO is formed2DMF solution;
(1-2) dissolving zirconium tetrachloride in TiO2Adding absolute ethyl alcohol into a DMF solution, and carrying out ultrasonic treatment;
(1-3) dissolving 2-amino terephthalic acid in TiO2In DMF solution, ultrasonic treatment;
(1-4) pouring the mixed solution obtained in the step (1-2) into the mixed solution obtained in the step (1-3), carrying out ultrasonic treatment, and carrying out heating reaction to obtain a reaction solution;
(1-5) centrifuging, washing and drying the reaction solution to finally obtain TiO2@ UiO-66-NH nanoparticles.
Further, TiO described in step (1-1)2The mass-volume ratio of the DMF to the DMF is (0.1-0.2) g:10 ml; zirconium tetrachloride and TiO described in step (1-2)2The mass-volume ratio of the DMF solution to the absolute ethyl alcohol is (0.1-0.15) g to 5ml (0.15-0.2) ml; 2-Aminoterephthalic acid and TiO described in step (1-3)2The mass-to-volume ratio of the DMF solution is (0.11-0.13) g:10 ml; in the step (1-4), the volume ratio of the mixed liquid obtained in the step (1-2) to the mixed liquid obtained in the step (1-3) is (3-5):10, the time of ultrasonic treatment is 20-40min, and the reaction temperature is 75-86 ℃; the temperature for drying in the step (1-5) is 115-125 ℃.
Further, the heating temperature of the casting solution is 50-90 ℃, and the standing and defoaming time is 20-25 h.
Furthermore, the thickness of the film formed by blade coating is controlled to be 100-250 μm.
Further, the gel bath is equal volume of absolute ethyl alcohol and deionized water, and the temperature of the gel bath is 15-25 ℃.
Further, the soaking time is 3-7 d.
A polyvinylidene fluoride mixed matrix membrane prepared as described above.
Compared with the prior art, the invention has the beneficial effects that:
(1) the invention makes nano-particle TiO2Uniformly coated on UiO-66-NH2Preparing a nano material TiO with photocatalysis and anti-pollution performance2@UiO-66-NH2The nano particles and PVDF have good compatibility and dispersibility, the ultrafiltration membrane prepared by the method has stronger anti-fouling capability, and can efficiently remove Cr (VI) in sewage;
(2) the prepared film has enhanced hydrophilicity and increased pure water flux, and simultaneously has excellent pollution resistance in the OVA treatment process, and has better photocatalysis effect on Cr (VI) under visible light;
(3) in the film of the invention, TiO2And UiO-66-NH2The synergistic effect of the two components can lead TiO to2Generates more photo-generated electrons and holes under illumination, obtains better photocatalysis performance, and is TiO2@UiO-66-NH2The nano particles and PVDF have good compatibility and dispersibility, TiO2@UiO-66-NH2The addition of the nanoparticles increases the hydrophilicity of the membrane and reduces the surface roughness of the membrane, thereby improving the anti-fouling capability of the membrane.
Drawings
FIG. 1 is a bar graph of flux recovery for membranes of the present invention;
FIG. 2 is a graph of catalytic efficiency for example 2;
FIG. 3 is a SEM cross-sectional view of example 2.
Detailed Description
The invention is described in detail below with reference to the figures and specific embodiments.
TiO2The @ UiO-66-NH nano-particles are prepared by the following steps:
(1) 0.25g of TiO2Adding the particles into 20mL of DMF, and magnetically stirring for 24h at normal temperature to form TiO2DMF solution;
(2) 0.126g of zirconium tetrachloride was dissolved in 5mL of TiO2Adding 0.17mL of absolute ethyl alcohol into a DMF solution, and carrying out ultrasonic treatment for 25 min;
(3) 0.136g of 2-amino terephthalic acid was dissolved in 10mL of TiO2In DMF solution, carrying out ultrasonic treatment for 25 min;
(4) after full dissolution, pouring the step (2) into the step (3), performing ultrasonic treatment for 30min, pouring into a reaction kettle, and placing in an oven at 80 ℃ for reaction;
(5) centrifuging the step (4), washing with DMF for 1 time, washing with ethanol for 3 times, drying in an oven at 120 deg.C to obtain TiO2@UiO-66-NH2A nanoparticle;
example 1
A preparation method of a polyvinylidene fluoride mixed matrix membrane comprises the following steps:
(1) TiO to be obtained2@UiO-66-NH2Dissolving the nano particles and PVDF in DMF to obtain a casting solution, wherein the mass ratio of the components is PVDF: TiO 22@UiO-66-NH2：PVP＝17:0.1:1；
(2) Stirring the casting solution prepared in the step (1) at 60 ℃ to fully dissolve the casting solution, and standing for defoaming for 24 hours;
(3) scraping the casting solution obtained in the step (2) to a film with the thickness of 150 microns on a glass plate;
(4) immersing the glass plate with the membrane liquid in the step (3) into a mixed solution of absolute ethyl alcohol and deionized water with the same volume at 15 ℃ for phase separation;
(5) and (4) transferring the membrane subjected to phase separation in the step (4) into deionized water, soaking for 3-7d to remove redundant solvent to obtain a polyvinylidene fluoride mixed matrix membrane, and then placing the polyvinylidene fluoride mixed matrix membrane into clean deionized water for storage so as to facilitate subsequent tests.
Example 2
A preparation method of a polyvinylidene fluoride mixed matrix membrane comprises the following steps:
(1) TiO to be obtained2@UiO-66-NH2Dissolving the nano particles and PVDF in DMF to obtain a casting solution, wherein the mass ratio of the components is PVDF: TiO 22@UiO-66-NH2：PVP＝17:0.5:1；
(2) Stirring the casting solution prepared in the step (1) at 70 ℃ to fully dissolve the casting solution, and standing and defoaming for 24 hours;
(3) scraping the casting solution obtained in the step (2) to a film with the thickness of 200 mu m on a glass plate;
(4) immersing the glass plate with the membrane liquid in the step (3) into a mixed solution of absolute ethyl alcohol and deionized water with the same volume at 20 ℃ for phase separation;
(5) and (4) transferring the membrane subjected to phase separation in the step (4) into deionized water, soaking for 3-7d to remove redundant solvent to obtain a polyvinylidene fluoride mixed matrix membrane, and then placing the polyvinylidene fluoride mixed matrix membrane into clean deionized water for storage so as to facilitate subsequent tests.
Example 3
A preparation method of a polyvinylidene fluoride mixed matrix membrane comprises the following steps:
(1) TiO to be obtained2@UiO-66-NH2Nanoparticles anddissolving PVDF in DMF to obtain a casting solution, wherein the mass ratio of the components is PVDF: TiO 22@UiO-66-NH2：PVP＝17:1:1；
(2) Stirring the casting solution prepared in the step (1) at 80 ℃ to fully dissolve the casting solution, and standing for defoaming for 24 hours;
(3) scraping the casting solution obtained in the step (2) to a film with the thickness of 250 microns on a glass plate;
(4) immersing the glass plate with the membrane liquid in the step (3) into a mixed solution of absolute ethyl alcohol and deionized water with the same volume at 25 ℃ for phase separation;
(5) and (4) transferring the membrane subjected to phase separation in the step (4) into deionized water, soaking for 3-7d to remove redundant solvent to obtain a polyvinylidene fluoride mixed matrix membrane, and then placing the polyvinylidene fluoride mixed matrix membrane into clean deionized water for storage so as to facilitate subsequent tests.
1. Performance test experiment
Testing anti-pollution performance
The recovery rate data of 0.5g/L Ovalbumin (OVA) salt solution flux were collected by a cross-flow filtration apparatus, self-made in the laboratory, at 0.1 MPa. Data were collected after each film was pre-stressed for 30min by DI to ensure accuracy, data being stable values obtained for more than three measurements per film. The test results are shown in figure 1.
② test of catalytic Performance
By K2Cr2O7The water solution is subjected to the photocatalytic reduction of Cr (VI) at normal temperature, the initial volume of the solution is 50.0mL, and the initial concentration is C0Is 5.0mg L-1. The suspension was irradiated for 120min under visible light provided by an LED with 50mW of optical power. The residual Cr (VI) concentration can be measured by diphenylcarbazide colorimetry, and Ct is the concentration of Cr (VI) in the permeate at time t. The test results are shown in FIG. 2.
2. And (3) performance test results:
as can be seen from FIG. 1, example 2 exhibited the best anti-fouling performance because OVA flux recovery was as high as 99.2% with TiO2@UiO-66-NH2With increasing addition, OVA flux recovery decreased, due to TiO2@UiO-66-NH2When the amount of (B) is large, although hydrophilicity is increased, the roughness of the film is increasedThere is also an increasing trend and the effect of this phenomenon on the fouling resistance of the membrane is greater. As can be seen from the attached figure 2, when the mass ratio of the components of the casting solution is PVDF: TiO 22@UiO-66-NH2: the catalytic reduction rate of example 2 to cr (vi) was 91.8% at PVP 17:0.5:1 and a test time of 120 minutes, as shown in fig. 2-3.
The foregoing is directed to preferred embodiments of the present invention, other and further embodiments of the invention may be devised without departing from the basic scope thereof, and the scope thereof is determined by the claims that follow. However, any simple modification, equivalent change and modification of the above embodiments according to the technical essence of the present invention are within the protection scope of the technical solution of the present invention.
Claims (10)
1. A preparation method of a polyvinylidene fluoride mixed matrix film is characterized by comprising the following steps: preparing the TiO obtained by a solvothermal method2@UiO-66-NH2The nano particles and PVP are added into PVDF as additives to prepare TiO2@UiO-66-NH2The PVDF membrane casting solution is prepared into a polyvinylidene fluoride mixed matrix membrane by adopting a non-solvent induced phase separation method.
2. The method for preparing polyvinylidene fluoride mixed matrix membrane according to claim 1, comprising the steps of:
(1) according to the mass ratio, the TiO prepared by the solvothermal method2@UiO-66-NH2Dissolving the nano particles and PVDF in DMF to obtain a membrane casting solution;
(2) heating and stirring the casting solution, and standing for defoaming;
(3) coating the defoamed casting solution on a plate to form a film;
(4) immersing the plate with the membrane in a gel bath for phase separation;
(5) and soaking the membrane after phase separation in deionized water to obtain the polyvinylidene fluoride mixed matrix membrane.
3. The method of claim 1, wherein the TiO is selected from the group consisting of2@UiO-66-NH2The mass ratio of PVP to PVDF is 1 (0.1-1) to 17.
4. The method of claim 1, wherein the TiO is selected from the group consisting of2The @ UiO-66-NH nano-particles are prepared by the following steps:
(1-1) mixing TiO2The particles are added to DMF and, after stirring, TiO is formed2DMF solution;
(1-2) dissolving zirconium tetrachloride in TiO2Adding absolute ethyl alcohol into a DMF solution, and carrying out ultrasonic treatment;
(1-3) dissolving 2-amino terephthalic acid in TiO2In DMF solution, ultrasonic treatment;
(1-4) pouring the mixed solution obtained in the step (1-2) into the mixed solution obtained in the step (1-3), carrying out ultrasonic treatment, and carrying out heating reaction to obtain a reaction solution;
(1-5) centrifuging, washing and drying the reaction solution to finally obtain TiO2@ UiO-66-NH nanoparticles.
5. A method for preparing polyvinylidene fluoride mixed matrix membrane according to claim 4, wherein the TiO compound in step (1-1)2The mass-volume ratio of the DMF to the DMF is (0.1-0.2) g:10 ml; zirconium tetrachloride and TiO described in step (1-2)2The mass-volume ratio of the DMF solution to the absolute ethyl alcohol is (0.1-0.15) g to 5ml (0.15-0.2) ml; 2-Aminoterephthalic acid and TiO described in step (1-3)2The mass-to-volume ratio of the DMF solution is (0.11-0.13) g:10 ml; in the step (1-4), the volume ratio of the mixed liquid obtained in the step (1-2) to the mixed liquid obtained in the step (1-3) is (3-5):10, the time of ultrasonic treatment is 20-40min, and the reaction temperature is 75-86 ℃; the temperature for drying in the step (1-5) is 115-125 ℃.
6. The preparation method of a polyvinylidene fluoride mixed matrix membrane according to claim 2, wherein the heating temperature of the membrane casting solution is 50-90 ℃, and the standing and defoaming time is 20-25 h.
7. The method for preparing a polyvinylidene fluoride mixed matrix membrane according to claim 2, wherein the thickness of the doctor-blade coating film is controlled to be 100-250 μm.
8. The method of claim 2, wherein the gelling bath is equal volume of absolute ethanol and deionized water, and the temperature of the gelling bath is 15-25 ℃.
9. The method of claim 2, wherein the soaking time is 3-7 days.
10. A polyvinylidene fluoride mixed matrix membrane prepared according to the method of any one of claims 1-9.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114849499A (en) * | 2022-05-18 | 2022-08-05 | 南京工大膜应用技术研究所有限公司 | Preparation method of modified PVDF (polyvinylidene fluoride) film applied to organophosphorus pesticide wastewater treatment |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108479424A (en) * | 2018-04-02 | 2018-09-04 | 合肥国轩高科动力能源有限公司 | A kind of preparation method of modified polyvinilidene fluoride film |
| CN110152741A (en) * | 2019-05-28 | 2019-08-23 | 浙江天蓝环保技术股份有限公司 | A kind of high efficiency composition visible light catalyst of core-shell structure and its preparation method and application |
| WO2019186134A1 (en) * | 2018-03-29 | 2019-10-03 | G2O Water Technologies Limited | Membranes comprising a layer of metal organic framework particles |
| CN111468147A (en) * | 2020-05-25 | 2020-07-31 | 浙江倪阮新材料有限公司 | Porous carbon composite titanium dioxide-oxyhalide photocatalyst and preparation method thereof |
| CN111495206A (en) * | 2020-05-09 | 2020-08-07 | 山东中莱新材料技术有限公司 | Preparation method of high-flux pressure-resistant ultrafiltration membrane |
-
2020
- 2020-08-10 CN CN202010795752.7A patent/CN112007523A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2019186134A1 (en) * | 2018-03-29 | 2019-10-03 | G2O Water Technologies Limited | Membranes comprising a layer of metal organic framework particles |
| CN108479424A (en) * | 2018-04-02 | 2018-09-04 | 合肥国轩高科动力能源有限公司 | A kind of preparation method of modified polyvinilidene fluoride film |
| CN110152741A (en) * | 2019-05-28 | 2019-08-23 | 浙江天蓝环保技术股份有限公司 | A kind of high efficiency composition visible light catalyst of core-shell structure and its preparation method and application |
| CN111495206A (en) * | 2020-05-09 | 2020-08-07 | 山东中莱新材料技术有限公司 | Preparation method of high-flux pressure-resistant ultrafiltration membrane |
| CN111468147A (en) * | 2020-05-25 | 2020-07-31 | 浙江倪阮新材料有限公司 | Porous carbon composite titanium dioxide-oxyhalide photocatalyst and preparation method thereof |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114849499A (en) * | 2022-05-18 | 2022-08-05 | 南京工大膜应用技术研究所有限公司 | Preparation method of modified PVDF (polyvinylidene fluoride) film applied to organophosphorus pesticide wastewater treatment |
| CN114849499B (en) * | 2022-05-18 | 2023-05-02 | 南京工大膜应用技术研究所有限公司 | Preparation method of modified PVDF (polyvinylidene fluoride) membrane applied to organophosphorus pesticide wastewater treatment |
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