CN117181025A - Defect MOFs-based self-cleaning ultrafiltration membrane material and preparation method and application thereof - Google Patents
Defect MOFs-based self-cleaning ultrafiltration membrane material and preparation method and application thereof Download PDFInfo
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- 239000012528 membrane Substances 0.000 title claims abstract description 66
- 230000007547 defect Effects 0.000 title claims abstract description 56
- 238000004140 cleaning Methods 0.000 title claims abstract description 55
- 238000000108 ultra-filtration Methods 0.000 title claims abstract description 46
- 239000000463 material Substances 0.000 title claims abstract description 26
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
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- 229940088710 antibiotic agent Drugs 0.000 claims abstract description 14
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- 238000000034 method Methods 0.000 claims abstract description 9
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- 239000010936 titanium Substances 0.000 claims description 17
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 16
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims description 16
- 229910052751 metal Inorganic materials 0.000 claims description 15
- 239000002184 metal Substances 0.000 claims description 14
- 150000003839 salts Chemical class 0.000 claims description 12
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 11
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 11
- 238000004090 dissolution Methods 0.000 claims description 10
- GPNNOCMCNFXRAO-UHFFFAOYSA-N 2-aminoterephthalic acid Chemical compound NC1=CC(C(O)=O)=CC=C1C(O)=O GPNNOCMCNFXRAO-UHFFFAOYSA-N 0.000 claims description 8
- 238000006243 chemical reaction Methods 0.000 claims description 8
- 238000001816 cooling Methods 0.000 claims description 8
- 239000008367 deionised water Substances 0.000 claims description 8
- 229910021641 deionized water Inorganic materials 0.000 claims description 8
- 239000011259 mixed solution Substances 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 8
- 239000004745 nonwoven fabric Substances 0.000 claims description 8
- -1 polytetrafluoroethylene Polymers 0.000 claims description 8
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 8
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 8
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 8
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 8
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 8
- 239000000843 powder Substances 0.000 claims description 8
- 239000002244 precipitate Substances 0.000 claims description 8
- 239000002904 solvent Substances 0.000 claims description 8
- 229910001220 stainless steel Inorganic materials 0.000 claims description 8
- 239000010935 stainless steel Substances 0.000 claims description 8
- 239000000725 suspension Substances 0.000 claims description 8
- 238000005303 weighing Methods 0.000 claims description 8
- 239000013179 MIL-101(Fe) Substances 0.000 claims description 7
- 239000013215 MIL-88B Substances 0.000 claims description 7
- 239000013207 UiO-66 Substances 0.000 claims description 7
- 238000001291 vacuum drying Methods 0.000 claims description 5
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 claims description 4
- 239000003054 catalyst Substances 0.000 claims description 4
- 239000003795 chemical substances by application Substances 0.000 claims description 4
- 238000011068 loading method Methods 0.000 claims description 4
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- 229920001223 polyethylene glycol Polymers 0.000 claims description 4
- 229920000642 polymer Polymers 0.000 claims description 4
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 claims description 4
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 3
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 3
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 claims description 3
- 229910000360 iron(III) sulfate Inorganic materials 0.000 claims description 3
- CMOAHYOGLLEOGO-UHFFFAOYSA-N oxozirconium;dihydrochloride Chemical compound Cl.Cl.[Zr]=O CMOAHYOGLLEOGO-UHFFFAOYSA-N 0.000 claims description 3
- DUNKXUFBGCUVQW-UHFFFAOYSA-J zirconium tetrachloride Chemical compound Cl[Zr](Cl)(Cl)Cl DUNKXUFBGCUVQW-UHFFFAOYSA-J 0.000 claims description 3
- 239000004695 Polyether sulfone Substances 0.000 claims description 2
- 239000002202 Polyethylene glycol Substances 0.000 claims description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 2
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 2
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- 238000000576 coating method Methods 0.000 claims description 2
- UXGNZZKBCMGWAZ-UHFFFAOYSA-N dimethylformamide dmf Chemical group CN(C)C=O.CN(C)C=O UXGNZZKBCMGWAZ-UHFFFAOYSA-N 0.000 claims description 2
- 239000010411 electrocatalyst Substances 0.000 claims description 2
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- 229910052726 zirconium Inorganic materials 0.000 claims description 2
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- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
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- 238000001179 sorption measurement Methods 0.000 description 1
- 229960002135 sulfadimidine Drugs 0.000 description 1
- ASWVTGNCAZCNNR-UHFFFAOYSA-N sulfamethazine Chemical compound CC1=CC(C)=NC(NS(=O)(=O)C=2C=CC(N)=CC=2)=N1 ASWVTGNCAZCNNR-UHFFFAOYSA-N 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
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- Separation Using Semi-Permeable Membranes (AREA)
Abstract
The application discloses a defect MOFs (metal organic frameworks) based self-cleaning ultrafiltration membrane material, a preparation method and application thereof. The prepared ultrafiltration membrane material has excellent electrocatalytic activity and anti-pollution performance, and can efficiently degrade new pollutants such as antibiotics in water under the assistance of electricity. The pore structure and the physicochemical properties of the defect MOFs are regulated and controlled in a competitive coordination mode, the hydrophilicity and the electrocatalytic activity of the defect MOFs-based ultrafiltration membrane are improved, and the membrane flux, the pollutant removal capability, the self-cleaning capability and the stability are effectively improved under low energy consumption. The preparation method specifically provides a method for preparing the defect MOFs self-cleaning ultrafiltration membrane by means of competitive coordination for the first time, and has wide application prospects in the fields of new pollutant treatment, sewage regeneration and the like.
Description
Technical Field
The application relates to the technical field of preparation of electroactive ultrafiltration membranes, in particular to a defect MOFs-based self-cleaning ultrafiltration membrane material, and a preparation method and application thereof.
Background
The special treatment of the urban sewage as reclaimed water to replace the conventional water resource can relieve the problem of water resource shortage, and the urban sewage is recycled, so that the method has obvious social benefit, environmental benefit and economic benefit. The device can save fresh water resources, reduce sewage discharge, reduce water environment pollution and simultaneously relieve overload operation of urban sewer. The water quality safety is the core and key place for guaranteeing the reuse of the reclaimed water. However, frequent detection of multiple antibiotics in reclaimed water creates increasingly serious bacterial resistance problems.
Membrane technology, particularly ultrafiltration, plays an important role in the utilization of reclaimed water due to its advantages of high efficiency, small footprint and relatively low energy consumption. However, ultrafiltration membranes have a much larger pore size than antibiotics and have poor retention properties for antibiotics. In addition, membrane fouling problems caused by the deposition of contaminants on the membrane are critical issues limiting the application of ultrafiltration membranes. The membrane material with electric activity can degrade pollutants through active oxygen species generated in situ on the membrane, and can endow the ultrafiltration membrane with pollutant removal and self-cleaning capabilities. The Metal Organic Frameworks (MOFs) are porous crystalline materials formed by connecting metal centers and organic ligands in a self-assembly mode, and have the advantages of large surface area, high porosity, easiness in functionalization, good water stability, rich metal active centers and the like. Through defect regulation and control, the pore structure of MOFs is changed, new active sites are generated, the electrocatalytic activity and conductivity of the MOFs can be enhanced, and the adsorption performance of the MOFs to pollutants is improved, so that the removal of antibiotics and the membrane pollution control performance of the defect MOFs-based ultrafiltration membrane are promoted.
Disclosure of Invention
The technical problems to be solved are as follows:
the application aims to solve the technical problems that the traditional ultrafiltration membrane has poor removal performance on new pollutants such as antibiotics and serious membrane pollution and the like, and provides a defect MOFs-based self-cleaning ultrafiltration membrane material, a preparation method and application thereof. The prepared membrane material has higher membrane flux and electrocatalytic performance, and can efficiently remove new pollutants such as antibiotics and the like and effectively control membrane pollution under the conditions of electric assistance and low energy consumption.
The technical scheme is as follows:
a preparation method of a defect MOFs-based self-cleaning ultrafiltration membrane material comprises the following specific process conditions:
the first step: weighing 3.3-13.2 mmol of amino terephthalic acid and 13.2-3.3 mmol of terephthalic acid, mixing the organic ligand and metal salt in a molar ratio of 1-1.5 in 36-72 mL of DMF solvent, adding 4-8 mL of methanol into the solution after complete dissolution, and stirring at constant speed until the solution is clear and transparent;
and a second step of: transferring the mixed solution suspension into a stainless steel high-pressure reaction kettle with a polytetrafluoroethylene lining of 100mL, and reacting for 48 hours at 150 ℃;
and a third step of: naturally cooling to room temperature, cleaning the obtained MOFs powder with DMF and ethanol solution for three times respectively to remove residual organic ligands and metal salts, centrifuging to collect the obtained precipitate, and vacuum drying at 80deg.C for 12 hr to obtain defective MOFs;
fourth step: adding 7.54-15.08 g of high polymer, 1g of pore-forming agent and 50mL of organic solvent into a three-neck flask, stirring for 48h under the constant temperature condition to form polyvinylidene fluoride solution, adding 9.4-1.88 g of graphite powder and 0.754-1.51 g of defect MOFs, fully stirring for 24h, standing for 24h for defoaming treatment, coating the porous support layer by a scraper of a film coater after standing and defoaming, immediately immersing in deionized water, and fully replacing and ten times to obtain the defect MOFs-based self-cleaning ultrafiltration membrane material.
Further, the metal salt in the first step is zirconium chloride, zirconium oxychloride, ferric sulfate, ferric chloride, tetrabutyl titanate or titanium isopropoxide; fourthly, the high molecular polymer is polyvinylidene fluoride PVDF and/or polyether sulfone, the pore-forming agent is polyvinylpyrrolidone and/or polyethylene glycol PEG, the organic solvent is N, N dimethylformamide DMF, the dissolution temperature is 65 ℃ and the time is 48 hours; the casting solution is defoamed at the constant temperature of 65 ℃.
The application also discloses the defect MOFs self-cleaning ultrafiltration membrane material prepared by the preparation method, wherein the defect MOFs self-cleaning ultrafiltration membrane material comprises a defect MOFs catalyst and a porous ultrafiltration membrane material combined with the defect MOFs catalyst, and the loading capacity of the MOFs is 0.377g-2.262g; the loading of the graphite powder is 0.94g-2.82g; the defective MOFs act as electrocatalysts.
As a preferred technical scheme of the application: the defect MOFs are selected from zirconium-based, titanium-based and iron-based MOFs, wherein the zirconium-based is UiO-66 (Zr) or MOF-808 (Zr), and the titanium-based is MIL-125 (Ti) or NH 2 MIL-125 (Ti), the iron base is MIL-88B (Fe) or MIL-101 (Fe).
As a preferred technical scheme of the application: the porous support layer is selected from commercial nonwoven fabrics.
As a preferred technical scheme of the application: the film thickness was 400. Mu.m.
The application of a defective MOFs-based self-cleaning ultrafiltration membrane material in removing trace antibiotics in sewage, wherein the sewage is urban sewage.
The technical principle of the application is as follows: through a simple joint competition coordination strategy, the defect MOFs with adjustable missing joint defects and graded holes are developed, and the defect MOFs-based self-cleaning ultrafiltration membrane can remarkably improve the electrocatalytic activity to tetracycline along with the introduction of moderate missing connector defects in the MOFs. In addition, the hierarchical porous nature of defective MOFs promotes water permeability and mass transfer of tetracyclines to active sites on the defective MOFs-based self-cleaning ultrafiltration membranes. Owing to the synergistic effect of the defects and the pores, the defect MOFs self-cleaning ultrafiltration membrane has good water flux, antibiotic removal and electric self-cleaning capability.
The beneficial effects are that:
compared with the prior art, the defect MOFs-based self-cleaning ultrafiltration membrane material and the preparation method and application thereof have the following technical effects:
1. the preparation method prepares the defect MOFs by a competitive coordination strategy and a hydrothermal synthesis method, and is simple to operate and easy to regulate and control. According to the application, defects are introduced in a mode of competing coordination between two organic ligands and a single metal center, so that the crystal structure and defect degree of MOFs are effectively regulated and controlled, and the degradation efficiency and self-cleaning performance of the defect MOFs-based ultrafiltration membrane on new pollutants such as antibiotics are improved;
2. the defect MOFs is used for modifying the ultrafiltration membrane, so that the water flux is improved, and the pollutants enriched on the membrane are degraded in situ under the assistance of electricity, so that the membrane has good anti-pollution and self-cleaning properties;
3. the defect MOFs-based ultrafiltration membrane prepared by the method has good repeatability and long service life, can meet the requirement of sewage recycling, still keeps 90% removal rate after six times of continuous use, and can still keep stable after long-time operation;
4. the defect MOFs-based self-cleaning ultrafiltration membrane material disclosed by the application has the advantages that the water flux of the membrane is improved by 52%, and the removal rate of tetracycline is improved by more than 40%.
Drawings
FIG. 1 is a scanning electron microscope image of a defective MOFs-based ultrafiltration membrane of the present application;
FIG. 2 shows the removal rate of tetracycline from defective MOFs-based ultrafiltration membranes;
FIG. 3 is a graph of membrane pollution control performance of a defective MOFs-based ultrafiltration membrane;
FIG. 4 is a graph of the reusability of defective MOFs-based ultrafiltration membranes.
Detailed Description
The application will be explained in more detail below with reference to specific embodiments, it being noted that the embodiments listed are not all but a part of them. The parts of the description of the embodiments of the application that are not explained in detail are common to those skilled in the art.
Example 1:
a preparation method of a defective MIL-125 (Ti) base electro-catalysis self-cleaning film comprises the following specific process conditions:
the first step: weighing 3.3-13.2 mmol of amino terephthalic acid and 13.2-3.3 mmol of terephthalic acid, mixing the organic ligand and tetrabutyl titanate in a molar ratio of 1-1.5 in 36-72 mL of DMF solvent, adding 4-8 mL of methanol into the solution after complete dissolution, and stirring at constant speed until the solution is clear and transparent;
and a second step of: transferring the mixed solution suspension into a stainless steel high-pressure reaction kettle with a polytetrafluoroethylene lining of 100mL, and reacting for 48 hours at 150 ℃;
and a third step of: naturally cooling to room temperature, washing the obtained MOFs powder with DMF and ethanol solution for three times respectively to remove residual organic ligand and metal salt, centrifuging to collect the obtained precipitate, and vacuum drying at 80deg.C for 12 hr to obtain defective MIL-125 (Ti);
fourth, a defective MIL-125 (Ti) -based electrocatalytic self-cleaning film was made in a three-neck flask:
s1, dissolving 7.54g of polyvinylidene fluoride and 1g of polyvinylpyrrolidone in 50mL of N, N dimethylformamide, and fully stirring for 48 hours to prepare a polyvinylidene fluoride solution;
s2, adding 0.94g of graphite powder and 0.754g of defective MIL-125 (Ti) into the prepared polyvinylidene fluoride solution, fully stirring for 24 hours to prepare casting solution, and standing for 24 hours for defoaming treatment;
and S3, casting the prepared casting film liquid on the surface of the non-woven fabric by adopting a film coating machine, then adding the casting film liquid into deionized water, and soaking for 24 hours to perform phase inversion treatment to prepare the defect MIL-125 (Ti) base electro-catalytic self-cleaning film with the thickness of 400 mu m.
Example 2
The embodiment provides a preparation method of a defect UiO-66 (Zr) based electro-catalytic self-cleaning film, which comprises the following steps:
the first step: weighing 3.3-13.2 mmol of amino terephthalic acid and 13.2-3.3 mmol of terephthalic acid, mixing the organic ligand and zirconium chloride in a molar ratio of 1-1.5 in 36-72 mL of DMF solvent, adding 4-8 mL of methanol into the solution after complete dissolution, and stirring at constant speed until the solution is clear and transparent;
and a second step of: transferring the mixed solution suspension into a stainless steel high-pressure reaction kettle with a polytetrafluoroethylene lining of 100mL, and reacting for 48 hours at 150 ℃;
and a third step of: naturally cooling to room temperature, washing the obtained MOFs powder with DMF and ethanol solution for three times respectively to remove residual organic ligands and metal salts, collecting the obtained precipitate by centrifugation, and finally drying in vacuum at 80 ℃ for 12 hours to obtain defect UiO-66 (Zr);
fourth, a defective UiO-66 (Zr) -based electrocatalytic self-cleaning film was made in a three-neck flask:
s1, dissolving 7.54g of polyvinylidene fluoride solution and 1g of polyvinylpyrrolidone in 50mL of N, N dimethylformamide, and fully stirring for 48 hours to prepare the polyvinylidene fluoride solution;
s2, adding 1.88g of graphite powder and 0.754g of defect UiO-66 (Zr) into the prepared polyvinylidene fluoride solution, fully stirring for 24 hours to prepare casting solution, and standing for defoaming;
and S3, casting the prepared casting film liquid on the surface of the non-woven fabric by adopting a film coating machine, then adding the casting film liquid into deionized water, and soaking for 24 hours to perform phase inversion treatment to prepare the defect UiO-66 (Zr) based electro-catalytic self-cleaning film with the thickness of 400 mu m.
Example 3
The embodiment provides a preparation method of a defect MIL-101 (Fe) -based electrocatalytic self-cleaning film, which comprises the following steps:
the first step: weighing 3.3-13.2 mmol of amino terephthalic acid and 13.2-3.3 mmol of terephthalic acid, mixing the organic ligand and ferric sulfate in a molar ratio of 1-1.5 in 36-72 mL of DMF solvent, adding 4-8 mL of methanol into the solution after complete dissolution, and stirring at constant speed until the solution is clear and transparent;
and a second step of: transferring the mixed solution suspension into a stainless steel high-pressure reaction kettle with a polytetrafluoroethylene lining of 100mL, and reacting for 48 hours at 150 ℃;
and a third step of: naturally cooling to room temperature, washing the obtained MOFs powder with DMF and ethanol solution for three times respectively to remove residual organic ligands and metal salts, collecting the obtained precipitate by centrifugation, and finally drying in vacuum at 80 ℃ for 12 hours to obtain defective MIL-101 (Fe);
fourth, a defective MIL-101 (Fe) -based electrocatalytic self-cleaning film was made in a three-neck flask:
s1, dissolving 7.54g of polyvinylidene fluoride and 1g of polyvinylpyrrolidone in 50mL of N, N dimethylformamide, and fully stirring for 48 hours to prepare a polyvinylidene fluoride solution;
s2, adding 2.82g of graphite powder and 0.754g of defective MIL-101 (Fe) into the prepared polyvinylidene fluoride solution, fully stirring for 24 hours to prepare casting solution, and standing for defoaming treatment;
and S3, casting the prepared casting film liquid on the surface of the non-woven fabric by adopting a film coating machine, then adding the casting film liquid into deionized water, and soaking for 24 hours to perform phase inversion treatment to prepare the defect MIL-101 (Fe) base electro-catalytic self-cleaning film with the thickness of 400 mu m.
The electrocatalytic self-cleaning films of different addition amounts of defective MOFs were prepared in the same addition amount of graphite powder in examples 4 to 6 below, and the preparation method was the same as in examples 1 to 3, except that the defective MOFs in examples 1 to 4 were MOFs of the same defect degree.
Example 4
The embodiment provides a preparation method of a defect MIL-125 (Ti) base electro-catalysis self-cleaning film, which comprises the following steps:
the first step: weighing 3.3-13.2 mmol of amino terephthalic acid and 13.2-3.3 mmol of terephthalic acid, mixing the organic ligand and tetrabutyl titanate in a molar ratio of 1-1.5 in 36-72 mL of DMF solvent, adding 4-8 mL of methanol into the solution after complete dissolution, and stirring at constant speed until the solution is clear and transparent;
and a second step of: transferring the mixed solution suspension into a stainless steel high-pressure reaction kettle with a polytetrafluoroethylene lining of 100mL, and reacting for 48 hours at 150 ℃;
and a third step of: naturally cooling to room temperature, washing the obtained MOFs powder with DMF and ethanol solution for three times respectively to remove residual organic ligand and metal salt, centrifuging to collect the obtained precipitate, and vacuum drying at 80deg.C for 12 hr to obtain defective MIL-125 (Ti);
fourth, a defective MIL-125 (Ti) -based electrocatalytic self-cleaning film was made in a three-neck flask:
s1, dissolving 7.54g of polyvinylidene fluoride and 1g of polyvinylpyrrolidone in 50mL of N, N dimethylformamide, and fully stirring for 48 hours to prepare a polyvinylidene fluoride solution;
s2, adding 1.88g of graphite powder and 0.377g of defective MIL-125 (Ti) into the prepared polyvinylidene fluoride solution, fully stirring for 24 hours to prepare casting solution, and standing and defoaming;
and S3, casting the prepared casting film liquid on the surface of the non-woven fabric by adopting a film coating machine, then adding the casting film liquid into deionized water, and soaking for 24 hours to perform phase inversion treatment to prepare the defect MIL-125 (Ti) base electro-catalytic self-cleaning film with the thickness of 400 mu m.
Example 5
The embodiment provides a preparation method of a defect MOF-808 (Zr) based electro-catalytic self-cleaning film, which comprises the following steps:
the first step: weighing 3.3-13.2 mmol of amino terephthalic acid and 13.2-3.3 mmol of terephthalic acid, mixing the organic ligand and zirconium oxychloride in a molar ratio of 1-1.5 in 36-72 mL of DMF solvent, adding 4-8 mL of methanol into the solution after complete dissolution, and stirring at constant speed until the solution is clear and transparent;
and a second step of: transferring the mixed solution suspension into a stainless steel high-pressure reaction kettle with a polytetrafluoroethylene lining of 100mL, and reacting for 48 hours at 150 ℃;
and a third step of: naturally cooling to room temperature, washing the obtained MOFs powder with DMF and ethanol solution for three times respectively to remove residual organic ligands and metal salts, collecting the obtained precipitate by centrifugation, and finally drying in vacuum at 80 ℃ for 12 hours to obtain defective MOF-808 (Zr);
fourth, a defective MOF-808 (Zr) -based electrocatalytic self-cleaning film was made in a three-neck flask:
s1, dissolving 7.54g of polyvinylidene fluoride and 1g of polyvinylpyrrolidone in 50mL of N, N dimethylformamide, and fully stirring for 48 hours to prepare a polyvinylidene fluoride solution;
s2, adding 1.88g of graphite powder and 1.508g of defect MOF-808 (Zr) into the prepared polyvinylidene fluoride solution, fully stirring for 24 hours to prepare casting solution, and standing for defoaming treatment;
and S3, casting the prepared casting film liquid on the surface of the non-woven fabric by adopting a film coating machine, then adding the casting film liquid into deionized water, and soaking for 24 hours to perform phase inversion treatment to prepare the defect MOF-808 (Zr) based electro-catalytic self-cleaning film with the thickness of 400 mu m.
Example 6
The embodiment provides a preparation method of a defect MIL-88B (Fe) base electrocatalytic film, which comprises the following steps:
the first step: weighing 3.3-13.2 mmol of amino terephthalic acid and 13.2-3.3 mmol of terephthalic acid, mixing the organic ligand and ferric chloride in a molar ratio of 1-1.5 in 36-72 mL of DMF solvent, adding 4-8 mL of methanol into the solution after complete dissolution, and stirring at constant speed until the solution is clear and transparent;
and a second step of: transferring the mixed solution suspension into a stainless steel high-pressure reaction kettle with a polytetrafluoroethylene lining of 100mL, and reacting for 48 hours at 150 ℃;
and a third step of: naturally cooling to room temperature, cleaning the MOFs powder with DMF and ethanol solution for three times respectively to remove residual organic ligands and metal salts, centrifuging to collect the obtained precipitate, and vacuum drying at 80deg.C for 12 hr to obtain defective MIL-88B (Fe);
fourth, a defective MIL-88B (Fe) -based electrocatalytic self-cleaning film was made in a three-neck flask:
s1, dissolving 7.54g of polyvinylidene fluoride and 1g of polyvinylpyrrolidone in 50mL of N, N dimethylformamide, and fully stirring for 48 hours to prepare a polyvinylidene fluoride solution;
s2, adding 1.88g of graphite powder and 2.262g of defective MIL-88B (Fe) into the prepared polyvinylidene fluoride solution, fully stirring for 24 hours to prepare casting solution, and standing for defoaming treatment;
and S3, casting the prepared casting film liquid on the surface of the non-woven fabric by adopting a film coating machine, then adding the casting film liquid into deionized water, and soaking for 24 hours to perform phase inversion treatment to prepare the defect MIL-88B (Fe) based electro-catalytic self-cleaning film with the thickness of 400 mu m.
Electrocatalytic film Performance experiments
The initial concentration of antibiotics (tetracycline, sulfadimidine, etc.) used in the experiment was 5mg/L, and the electrolyte was 0.1M Na 2 SO 4 The antibiotic concentrations were measured by sampling at 5, 10, 20, 30, 60, 90 and 120min, respectively. The antibiotic removal effect was observed as a trend of the remaining antibiotic concentration over time. Normalized concentration c=c t /C 0 C represents normalized concentration, C t Indicating the residual concentration of antibiotics at different times, C 0 Indicating the initial concentration of antibiotic.
Experimental example 1
The self-cleaning ultrafiltration membrane prepared in example 1 was used as an anode in the current density of 0.02mA/cm 2 Is used for removing antibiotics in the water body, and the removal result of the antibiotics is shown in figure 2. Experimental results show that the removal rate of the embodiment 2 reaches more than 90%, and is improved by more than 40% compared with the original MIL-125 (Ti) self-cleaning ultrafiltration membrane.
Experimental example 2
The self-cleaning ultrafiltration membrane prepared in example 1 was used as an anode in the current density of 0.02mA/cm 2 Under the condition of taking BSA as model dirt, performing a membrane pollution experiment until the flux of the membrane is reduced to a certain value, and then electrifying and cleaning the polluted membrane for 30 minutes. Membrane flux was again observed and membrane fouling experiments were still performed with BSA as model fouling until membrane flux was again reduced. This was repeated twice, and recovery of membrane flux was observed. The experimental results show that the flux of the membrane can still be recovered to 90% in the third time of pollution.
Claims (7)
1. A preparation method of a defect MOFs-based self-cleaning ultrafiltration membrane material is characterized by comprising the following specific steps:
the first step: weighing 3.3-13.2 mmol of amino terephthalic acid and 13.2-3.3 mmol of terephthalic acid, mixing the organic ligand and metal salt in a molar ratio of 1-1.5 in 36-72 mL of DMF solvent, adding 4-8 mL of methanol into the solution after complete dissolution, and stirring at constant speed until the solution is clear and transparent;
and a second step of: transferring the mixed solution suspension into a stainless steel high-pressure reaction kettle with a polytetrafluoroethylene lining of 100mL, and reacting for 48 hours at 150 ℃;
and a third step of: naturally cooling to room temperature, cleaning the obtained MOFs powder with DMF and ethanol solution for three times respectively to remove residual organic ligands and metal salts, centrifuging to collect the obtained precipitate, and vacuum drying at 80deg.C for 12 hr to obtain defective MOFs;
fourth step: adding 7.54-15.08 g of high polymer, 1g of pore-forming agent and 50mL of organic solvent into a three-neck flask, stirring for 48h under the constant temperature condition to form polyvinylidene fluoride solution, adding 9.4-1.88 g of graphite powder and 0.754-1.51 g of defect MOFs, fully stirring for 24h, standing for 24h for defoaming treatment, coating the porous support layer by a scraper of a film coater after standing and defoaming, immediately immersing in deionized water, and fully replacing and ten times to obtain the defect MOFs-based self-cleaning ultrafiltration membrane material.
2. The method for preparing the defect MOFs-based self-cleaning ultrafiltration membrane material according to claim 1, wherein the metal salt in the first step is zirconium chloride, zirconium oxychloride, ferric sulfate, ferric chloride, tetrabutyl titanate or titanium isopropoxide; fourthly, the high molecular polymer is polyvinylidene fluoride PVDF and/or polyether sulfone, the pore-forming agent is polyvinylpyrrolidone and/or polyethylene glycol PEG, the organic solvent is N, N dimethylformamide DMF, the dissolution temperature is 65 ℃ and the time is 48 hours; the casting solution is defoamed at the constant temperature of 65 ℃.
3. A defective MOFs-based self-cleaning ultrafiltration membrane material prepared by the preparation method of claim 1 or 2, which is characterized in that: the defect MOFs-based self-cleaning ultrafiltration membrane material comprises a defect MOFs catalyst and a porous ultrafiltration membrane material combined with the defect MOFs catalyst, wherein the loading amount of the MOFs is 0.377g-2.262g; the loading of the graphite powder is 0.94g-2.82g; the defective MOFs act as electrocatalysts.
4. The defective MOFs-based self-cleaning ultrafiltration membrane material according to claim 3, wherein: the defect MOFs are selected from zirconium-based, titanium-based and iron-based MOFs, wherein the zirconium-based is UiO-66 (Zr) or MOF-808 (Zr), and the titanium-based is MIL-125 (Ti) or NH 2 MIL-125 (Ti), the iron base is MIL-88B (Fe) or MIL-101 (Fe).
5. The method for preparing the defect MOFs self-cleaning ultrafiltration membrane material according to claim 1, wherein the method is characterized by comprising the following steps: the porous support layer is selected from commercial nonwoven fabrics.
6. The defective MOFs-based self-cleaning ultrafiltration membrane material according to claim 3, wherein: the film thickness was 400. Mu.m.
7. Use of a defective MOFs-based self-cleaning ultrafiltration membrane material according to claim 3 for removing trace antibiotics from sewage, characterized in that: the sewage is urban sewage.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN117626533A (en) * | 2024-01-25 | 2024-03-01 | 石家庄铁道大学 | NH 2 Preparation method of MIL-125 filled dielectric film |
| CN117861452A (en) * | 2024-03-11 | 2024-04-12 | 深圳格立菲环境科技有限公司 | Hollow fiber ultrafiltration membrane and preparation method thereof |
| CN117861452B (en) * | 2024-03-11 | 2024-05-28 | 深圳格立菲环境科技有限公司 | Hollow fiber ultrafiltration membrane and preparation method thereof |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN117626533A (en) * | 2024-01-25 | 2024-03-01 | 石家庄铁道大学 | NH 2 Preparation method of MIL-125 filled dielectric film |
| CN117861452A (en) * | 2024-03-11 | 2024-04-12 | 深圳格立菲环境科技有限公司 | Hollow fiber ultrafiltration membrane and preparation method thereof |
| CN117861452B (en) * | 2024-03-11 | 2024-05-28 | 深圳格立菲环境科技有限公司 | Hollow fiber ultrafiltration membrane and preparation method thereof |
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