CN112915816A - MXene separation membrane capable of simultaneously separating oil and dye and preparation method and application thereof - Google Patents
MXene separation membrane capable of simultaneously separating oil and dye and preparation method and application thereof Download PDFInfo
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- 238000000926 separation method Methods 0.000 title claims abstract description 95
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- -1 carboxyl siloxane Chemical class 0.000 claims abstract description 29
- 238000000034 method Methods 0.000 claims abstract description 23
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- 239000000843 powder Substances 0.000 claims description 10
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 9
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- 238000005286 illumination Methods 0.000 claims description 7
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- 150000001875 compounds Chemical class 0.000 claims description 4
- KWVGIHKZDCUPEU-UHFFFAOYSA-N 2,2-dimethoxy-2-phenylacetophenone Chemical group C=1C=CC=CC=1C(OC)(OC)C(=O)C1=CC=CC=C1 KWVGIHKZDCUPEU-UHFFFAOYSA-N 0.000 claims description 2
- 239000011230 binding agent Substances 0.000 claims description 2
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- 239000000463 material Substances 0.000 abstract description 7
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- 125000000524 functional group Chemical group 0.000 abstract description 5
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- 239000000975 dye Substances 0.000 description 36
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- 230000004907 flux Effects 0.000 description 8
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- 238000012360 testing method Methods 0.000 description 4
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 3
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- RBTBFTRPCNLSDE-UHFFFAOYSA-N 3,7-bis(dimethylamino)phenothiazin-5-ium Chemical compound C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 RBTBFTRPCNLSDE-UHFFFAOYSA-N 0.000 description 2
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- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
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Images
Classifications
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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
- B01D67/0081—After-treatment of organic or inorganic membranes
- B01D67/0093—Chemical modification
-
- 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
-
- 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
- C02F1/40—Devices for separating or removing fatty or oily substances or similar floating material
-
- 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
- C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2325/00—Details relating to properties of membranes
- B01D2325/36—Hydrophilic membranes
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/308—Dyes; Colorants; Fluorescent agents
Abstract
The invention belongs to the field of material chemical industry, and discloses an MXene separation membrane capable of simultaneously separating oil and dye, and a preparation method and application thereof, wherein the preparation method comprises the following steps: (1) preparing MXene aqueous dispersion solution by a chemical stripping method; (2) preparing carboxyl siloxane solution by a photopolymerization method; (3) preparing MXene aqueous dispersion and polyvinyl alcohol adhesive into mixed solution, depositing the mixed solution on a PVDF membrane treated by ethanol, water and alkali liquor in sequence by a vacuum filtration method, spraying carboxyl siloxane solution on the surface of the membrane, and drying to obtain the organic modified MXene separation membrane. The separation membrane prepared by the invention has simple preparation process and low cost; the oil-in-water emulsion and the dye sewage can be efficiently and simultaneously separated, and the hydrophilic functional groups on the surface of the membrane endow the membrane with better oil/dye pollution resistance; the inherent mechanical properties of two-dimensional inorganic membranes impart more excellent durability to the membranes than organic separation membranes.
Description
Technical Field
The invention relates to the field of material chemical industry, in particular to an MXene separation membrane capable of simultaneously separating oil and dye, and a preparation method and application thereof.
Background
Water plays an important role in maintaining human life and sustainable social development. However, with the rapid growth of the population and the rapid development of the industry, water pollution also becomes more and more severe. Among the various water source pollutants, organic matter (such as various oils) and soluble organic matter (such as dyes) are the main pollutants, and these pollutants have the characteristics of non-biodegradability, high toxicity, carcinogenesis and even mutagenicity, and the discharge of the pollutants can cause serious threats to health and ecology. Therefore, the design of advanced separation materials has great strategic significance on the purification treatment of the sewage.
In recent decades, the membrane separation technology has the advantages of high separation efficiency, low cost and energy consumption, and is rapidly developed in the field of oil-water separation, however, most of the existing oil-water separation membranes only remove one type of pollutants, and for various pollutants, a plurality of equipment units are generally required to be connected in series to achieve the purpose of treating the various pollutants, and the process is complex, time-consuming and labor-consuming; in addition, in long-term filtration of the membrane, the oil/dye in water usually causes irreversible membrane contamination, which leads to a decrease in membrane flux, and the conventional organic separation membrane has poor mechanical resistance, which leads to a poor membrane durability, and thus a durable separation membrane material capable of separating oil and dye at the same time and having good antifouling performance is in demand.
Two-dimensional transition metal carbide (MXene) materials are recently researched and used for preparing 2D separation membrane materials due to unique atomic thickness, micron transverse size, mechanical property and rich surface chemical groups, and show excellent characteristics in the fields of gas separation, seawater desalination, sewage purification and the like. However, the separation membrane prepared by MXene has the problems of small quantity of surface functional groups, poor flexibility, single application function and the like, and the traditional organic polymer has controllable quantity and variety of functional groups and good ductility, so that an inorganic-organic composite oil-water separation membrane is urgently needed to be developed.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide an MXene separating membrane capable of simultaneously separating oil and dye as well as a preparation method and application thereof. The invention is based on the chemical composition of a two-dimensional material MXene and a nano sheet structure, the surface with a micro-nano structure is prepared by a vacuum filtration method, and further Mxene and a vinyl monomer containing carboxyl are bridged by a silane coupling agent chemical bond. The surface of the membrane has a large number of carboxyl, hydroxyl and other hydrophilic functional groups, so that the membrane has good separation and adsorption effects on various oil-in-water emulsions and dyes, has good antifouling property and durability, and can be used for treating complex sewage.
In order to achieve the purpose, the invention adopts the technical scheme that:
a preparation method of MXene separation membrane capable of simultaneously separating oil and dye comprises the following steps:
(1) preparing MXene aqueous dispersion solution by a chemical stripping method;
(2) preparing carboxyl siloxane solution by a photopolymerization method;
(3) preparing mixed solution of the MXene aqueous dispersion prepared in the step (1) and a polyvinyl alcohol adhesive, depositing the mixed solution on a PVDF membrane treated by ethanol, water and alkali liquor in sequence by a vacuum filtration method, spraying the carboxyl siloxane solution obtained in the step (2) on the surface of the membrane, and drying at 70-120 ℃ for 1-3 hours to obtain the MXene separation membrane for simultaneously separating oil and dye.
Preferably, the siloxane in the step (2) is gamma-Mercaptopropyltrimethoxysilane (MPTS), the carboxyl siloxane is at least one of a compound in a formula (I) and a compound in a formula (II),
preferably, the preparation of the carboxysiloxane solution of step (2): uniformly mixing siloxane, vinyl monomer containing carboxyl, photoinitiator and alcohol organic solvent (polarity: 3.7-4.3), and stirring to react under the condition of ultraviolet illumination to obtain a carboxyl siloxane solution; the photoinitiator is 2, 2-dimethoxy-2-phenylacetophenone (DMPA).
Preferably, the mass ratio of the MPTS and the carboxyl-containing vinyl monomer in the step (2) is 7: (3-5); the using amount of the photoinitiator is 3.5 +/-1.5 percent of the total monomer mass; the alcohol organic solvent is one of isopropanol, n-butanol or ethanol.
Preferably, the molecular weight of the polyvinyl alcohol binder in the step (3) is 16000, and the mass ratio of MXene to polyvinyl alcohol is (1-2): 1; the pore size of the PVDF membrane is preferably 0.22 micron; the loading capacity of the MXene on the membrane is 15mg m-2-30mg m-2(ii) a The spraying amount of the carboxyl siloxane is 1-3mL m-2。
Preferably, the preparation of the MXene aqueous dispersion solution in the step (1): adding MAX powder and lithium fluoride (LiF) slowly into a concentrated hydrochloric acid solution, stirring uniformly, etching at room temperature, centrifuging to obtain a multilayer MXene nanosheet, ultrasonically stripping the multilayer MXene nanosheet, and centrifuging to obtain a small-layer MXene aqueous dispersion solution.
Preferably, the particle size of the MAX powder in step (1) is 200-: (1-2); the stripped multilayer MXene is subjected to ultrasonic treatment in ethanol.
The invention also provides an organic modified MXene separation membrane prepared by any one of the methods.
The invention also provides application of the organic modified Mxene separation membrane in simultaneous separation of oil and dye wastewater.
The invention has the beneficial effects that:
1. the PVDF membrane adopted by the invention has excellent mechanical property and good chemical stability, MXene is deposited on the surface of the membrane by a vacuum filtration method, and simultaneously, a carboxyl siloxane solution and a super-hydrophilic-underwater super-oleophobic PVDF membrane are sprayed, grafted and fixed, and carboxyl siloxane is used as a chemical coupling agent, so that the combination of carboxyl and Mxene surface is firmer; the special two-dimensional layered structure of MXene endows the membrane with excellent separation efficiency and high flux.
2. The preparation method is simple and low in cost; the firmness of the MXene structure is improved by using the polyvinyl alcohol adhesive; and the hydrophilic functional group and the grafted carboxyl group on the MXene surface endow the membrane with the function of simultaneously separating oil and dye and blocking oil pollution of a hydration layer, so that the problems of single function and poor durability of the membrane are effectively solved, the prepared oil-water separation membrane continuously separates oil-containing dye sewage for 20 times, and the flux is still maintained at 1500L/(m) m2H.bar), the removal rate of the dye and the oil stain is still maintained to be more than 98 percent.
Drawings
Fig. 1 is an SEM image of etched MXene nanopowder prepared in example 1.
Fig. 2 is an SEM image of the Mxene separation membrane prepared in example 1.
FIG. 3 is a contact angle measurement of a separation membrane of Mxene separation membrane prepared in example 1, wherein a picture (a) of a water contact angle of the membrane in air is included; underwater oil (chloroform) contact angle picture of film (b).
FIG. 4 is a pictorial representation of the Mxene separation membrane prepared in example 1 before (a) and after (b) separation of hexadecane/Tween 80/water oil-in-water emulsion and the corresponding microscope picture.
Fig. 5 is a physical diagram of the Mxene separation membrane prepared in example 1 before (a) and after (b) the separation of oil and dye wastewater simultaneously and a corresponding microscopic picture.
FIG. 6 is the UV absorption spectra of MB before and after the Mxene separation membrane prepared in example 1 is subjected to simultaneous separation of oil and dye wastewater.
FIG. 7 is a graph of the flux of Mxene separation membrane and the original PVDF membrane prepared in example 1 as a function of the number of separation cycles.
FIG. 8 is a graph of oil and dye removal as a function of separation cycle number for the Mxene separation membrane prepared in example 1.
Detailed Description
The present invention will be further described with reference to the following specific examples.
Example 1
A preparation method of MXene separation membrane capable of simultaneously separating oil and dye comprises the following steps:
(1) MXene aqueous dispersion solution prepared by chemical stripping method
Slowly adding 1g of MAX powder with the particle size of 400 meshes and 1g of lithium fluoride (LiF) into 20mL of concentrated hydrochloric acid solution, uniformly stirring, etching at room temperature for 35h, centrifuging at 3500rpm for 3 times, centrifuging for 10min each time to obtain multilayer MXene nanosheets, then placing the multilayer MXene nanosheets into 100mL of ethanol, ultrasonically stripping for 1h, centrifuging at 8000rpm for 3 times, centrifuging for 30min each time to obtain a few-layer MXene water dispersible solution;
(2) preparation of a Carboxylic siloxane solution by photopolymerization
3.9g of 3-Mercaptopropyltrimethoxysilane (MPTS), 1.7g of methacrylic acid, 0.2g of DMPA and 20g of isopropanol (polarity: 4.3) are uniformly mixed and stirred to react for 1 hour under the condition of ultraviolet illumination to obtain a carboxyl siloxane solution;
(3) MXene separation membrane for preparing and simultaneously separating oil and dye
10mL (1) of the prepared MXene aqueous dispersion (3mg L)-1) And 0.03mg of polyvinyl alcohol (molecular weight 16000) were mixed, and deposited on a PVDF membrane (pore size: 0.22 micron; diameter: 5cm), then 1mL of the carboxysiloxane obtained in (2) was sprayed on the membrane surface, and after drying at 120 ℃ for 1h, an MXene separation membrane for simultaneous separation of oil and dye was obtained.
Example 2
(1) MXene aqueous dispersion solution prepared by chemical stripping method
Slowly adding 1g of MAX powder with the particle size of 200 meshes and 2g of lithium fluoride (LiF) into 20mL of concentrated hydrochloric acid solution, uniformly stirring, etching at room temperature for 35h, centrifuging at 3500rpm for 3 times, centrifuging for 10min each time to obtain a multilayer MXene nanosheet, then placing the multilayer MXene nanosheet into 100mL of ethanol, ultrasonically stripping for 1h, centrifuging at 8000rpm for 3 times, centrifuging for 30min each time to obtain a few-layer MXene water dispersible solution;
(2) preparation of a Carboxylic siloxane solution by photopolymerization
3.9g of 3-Mercaptopropyltrimethoxysilane (MPTS), 2.2g of methacrylic acid, 0.21g of DMPA and 20g of n-butanol (polarity: 3.7) are uniformly mixed and stirred to react for 2 hours under the condition of ultraviolet illumination to obtain a carboxyl siloxane solution;
(3) MXene separation membrane for preparing and simultaneously separating oil and dye
10mL (1) of the prepared MXene aqueous dispersion (4mg L)-1) And 0.03mg of polyvinyl alcohol (molecular weight 16000) were mixed, and deposited on a PVDF membrane (pore size: 0.22 micron; diameter: 5cm), then 3mL of the carboxysiloxane obtained in (2) was sprayed on the membrane surface, and after drying at 70 ℃ for 3h, an MXene separation membrane was obtained which separated oil and dye simultaneously.
Example 3
(1) MXene aqueous dispersion solution prepared by chemical stripping method
Slowly adding 1g of MAX powder with the particle size of 600 meshes and 1.5g of lithium fluoride (LiF) into 20mL of concentrated hydrochloric acid solution, uniformly stirring, etching at room temperature for 35h, centrifuging at 3500rpm for 3 times, centrifuging for 10min each time to obtain multilayer MXene nanosheets, then placing the multilayer MXene nanosheets into 100mL of ethanol, ultrasonically stripping for 1h, centrifuging at 8000rpm for 3 times, centrifuging for 30min each time to obtain a few-layer MXene water dispersible solution;
(2) preparation of a Carboxylic siloxane solution by photopolymerization
3.9g of 3-Mercaptopropyltrimethoxysilane (MPTS), 2.8g of acrylic acid, 0.23g of DMPA and 20g of ethanol (polarity: 4) are uniformly mixed and stirred to react for 3 hours under the condition of ultraviolet illumination to obtain a carboxyl siloxane solution;
(3) MXene separation membrane for preparing and simultaneously separating oil and dye
10mL (1) of the prepared MXene aqueous dispersion (6mg L)-1) And 0.03mg of polyvinyl alcohol (molecular weight 16000)And (3) combining the solution, depositing the solution on a PVDF membrane which is washed and alkalized in advance by a vacuum filtration method, then spraying 2mL of the carboxyl siloxane solution obtained in the step (2) on the surface of the membrane, and drying for 2h at 90 ℃ to obtain the MXene separation membrane for simultaneously separating oil and dye.
Example 4 (methanol as organic solvent)
(1) MXene aqueous Dispersion by chemical stripping (same as in example 1)
(2) Preparation of a Carboxylic siloxane solution by photopolymerization
3.9g of 3-Mercaptopropyltrimethoxysilane (MPTS), 1.7g of methacrylic acid, 0.2g of DMPA and 20g of methanol (polarity: 6.6) are uniformly mixed and stirred to react for 1 hour under the condition of ultraviolet illumination to obtain a carboxyl siloxane solution;
(3) preparation of MXene separation Membrane for Simultaneous separation of oil and dye (same as example 1)
Example 5 (photoinitiator benzophenone)
(1) MXene aqueous Dispersion by chemical stripping (same as in example 1)
(2) Preparation of a Carboxylic siloxane solution by photopolymerization
3.9g of 3-Mercaptopropyltrimethoxysilane (MPTS), 1.7g of methacrylic acid, 0.2g of benzophenone and 20g of isopropanol (polarity: 4.3) are uniformly mixed and stirred to react for 1 hour under the condition of ultraviolet illumination to obtain a carboxyl siloxane solution;
(3) an MXene separation membrane was prepared (same as example 1) to separate oil and dye simultaneously.
Example 6 (non-polyvinyl alcohol Adhesives)
(1) MXene aqueous Dispersion by chemical stripping (same as in example 1)
(2) Preparation of a Carboxylic siloxane solution by photopolymerization (same as in example 1)
(3) MXene separation membrane for preparing and simultaneously separating oil and dye
10mL (1) of the prepared MXene aqueous dispersion (5mg L)-1) The composite membrane is deposited on a PVDF membrane (aperture: 0.22 micron; diameter: 5cm), followed by spraying 2mL of the carboxysiloxane obtained in (2) onto the filmThe surface is dried for 2h at 100 ℃, and an MXene separation membrane for simultaneously separating oil and dye is obtained.
Experimental verification data for the technical effects of the examples are as follows.
1. Effect of alcohol organic solvent and photoinitiator species on the conversion of the Carboxylsiloxane Compound
The carboxy siloxane compounds prepared according to examples 1-6, using isopropanol, n-butanol and ethanol as solvents, and DMPA as photoinitiator gave more than 98% conversion, while using methanol as solvent and benzophenone as photoinitiator gave 34% and 45% conversion, respectively, indicating that the selection of alcoholic organic solvents with polarity range between 3.7 and 4.3, and the higher conversion of the carboxy siloxane compounds obtained with DMPA as photoinitiator, are given in table 1 below:
TABLE 1
2. Effect of polyvinyl alcohol on Water resistance of oil-Water separating Membrane
The oil-water separation membranes prepared in the examples 1 and 6 are soaked in water, the surface structure of the oil-water separation membrane prepared in the example 1 is still kept intact after the oil-water separation membrane is placed in water for 24 hours, and compared with the oil-water separation membrane prepared in the example 6, MXene falls off from the surface of the oil-water separation membrane after the oil-water separation membrane is soaked in water for 1 minute, the fastness of the MXene structure is improved by adding the polyvinyl alcohol.
3. SEM characterization of MXene separation membranes
From SEM figure 1 of the etched MAX powder prepared in example 1, it can be seen that the MAX powder has an excellent layered structure, and from figure 2, after MXene suction filtration and carboxyl siloxane spray coating, the membrane has a uniform layered wrinkle roughness structure, which gives the membrane excellent interface wettability and pore channels.
4. Contact angle of MXene separation membranes and oil-in-water emulsion separation test
The oil-water separation membranes prepared in examples 1 to 3 were used as the subjects, for exampleAs shown in fig. 3, the MXene separation membrane prepared in example 1 has a water contact angle of 0 ° in air and an oil contact angle of 153 ° under water, demonstrating excellent hydrophilicity and underwater oleophobicity of the separation membrane. The separation method is characterized in that hexadecane/Tween 80/water oil-in-water emulsion is used as a separation object, as can be seen from figure 4, the permeation liquid is obviously different from the original liquid, the original water-in-oil emulsion is milky and the oil drop size is large, the permeation liquid obtained after separation is clear and transparent and has no oil drop display, in addition, the separation efficiency tested by a total organic carbon analyzer is more than 99 percent, and the membrane flux can reach 1500L/(m) in the oil-water separation process2H.bar) above, it was demonstrated that the separation membrane prepared in example 1 has excellent separation efficiency for oil-in-water emulsions. The contact angle, flux and separation efficiency of the separation membranes prepared in examples 2 and 3 were the same as those of example 1, and the specific data are shown in table 2 below:
TABLE 2
| Performance of | Example 1 | Example 2 | Example 3 |
| Water contact angle in |
0° | 0° | 0° |
| Underwater oil contact angle | 153° | 154° | 152° |
| Flux L/(m)2.h.bar) | 1500 | 1523 | 1545 |
| Separation efficiency% | 99 | 99.1 | 99.2 |
5. Test for simultaneously separating oil and dye sewage by MXene separation membrane
Using the separation membranes prepared in examples 1 to 3 as the subjects, the separation membrane was subjected to a hexadecane/water/Tween 80 emulsified oil containing methylene blue MB (10mg/L) as the organic dye, and 35mL of the emulsion containing the organic dye was added to a vacuum filtration apparatus. By comparing the real object diagram and the microscopic diagram before and after the separation of fig. 5, the membrane has a better separation effect on the emulsion, in addition, by comparing the color change of the stock solution and the permeation solution, the light blue emulsion becomes transparent pure water, fig. 6 shows that the content of MB in the stock solution and the permeation solution is represented by ultraviolet/visible spectroscopy, the dye removal rate reaches more than 99 percent, which is mainly caused by the electrostatic interaction and hydrogen bonding of carboxyl on the membrane surface and hydroxyl on the MXene surface and dye molecules, the following table 2 gives the separation performance data of the separation membranes prepared in examples 1-3 on the oil-containing dye wastewater, and the above results prove that the separation membranes prepared in examples 1-3 exhibit excellent separation performance on complex wastewater.
TABLE 3
| Performance of | Example 1 | Example 2 | Example 3 |
| Flux L/(m)2.h.bar) | 1524 | 1535 | 1526 |
| Separation efficiency% | 99.1 | 99.4 | 99.1 |
| Dye removal Rate% | 99.2 | 99.7 | 99.4 |
6. MXene separation membrane antifouling and durability test
Using the separation membrane prepared in example 1 as an experimental subject, 35mL of emulsified oil of hexadecane/water/Tween 80 containing organic dye methylene blue MB (10mg/L) was poured into an oil-water separator, and the oil stain on the membrane surface was washed with water after each filtration and adsorbed with acid for 20 times. FIG. 7 shows that the flux of MXene separation membrane was always maintained at 1500L/(m) in the cycling test2H.bar), whereas for the original PVDF membrane the membrane flux drops to almost 0 over 3 filtration passes, mainly due to the separation membrane surface having a large number of hydrophilic groups and water molecules forming a hydration layer, thus blocking oil adhesion. Figure 8 shows that the oil and dye removal rate of the separation membrane was maintained above 98% in the recycle test. In conclusion, the MXene separation membrane prepared in example 1 has better antifouling property and durability.
The MXene separation membranes prepared in examples 2 and 3 also have similar technical effects to those of example 1 in the measurement of antifouling and durability properties of the membranes.
Although the present invention has been described in detail with reference to the preferred embodiments, it will be understood by those skilled in the art that various changes may be made and equivalents may be substituted for elements thereof without departing from the true spirit and scope of the present invention.
Claims (10)
1. A preparation method of MXene separation membrane capable of simultaneously separating oil and dye is characterized by comprising the following steps:
(1) preparing MXene aqueous dispersion solution by a chemical stripping method;
(2) preparing carboxyl siloxane solution by a photopolymerization method;
(3) preparing mixed solution of the MXene aqueous dispersion prepared in the step (1) and a polyvinyl alcohol adhesive, depositing the mixed solution on a PVDF membrane treated by ethanol, water and alkali liquor in sequence by a vacuum filtration method, spraying the carboxyl siloxane solution obtained in the step (2) on the surface of the membrane, and drying to obtain the MXene separation membrane.
2. The method according to claim 1, wherein the siloxane of step (2) is gamma-Mercaptopropyltrimethoxysilane (MPTS), the carboxyl siloxane is at least one of a compound of formula (I) and a compound of formula (II),
3. the preparation method according to claim 2, characterized in that the preparation of the carboxysiloxane solution of step (2): uniformly mixing siloxane, a vinyl monomer containing carboxyl, a photoinitiator and an alcohol organic solvent with the polarity of 3.7-4.3, and stirring and reacting under the condition of ultraviolet illumination to obtain a carboxyl siloxane solution; the photoinitiator is 2, 2-dimethoxy-2-phenylacetophenone (DMPA).
4. The method according to claim 3, wherein the mass ratio of the MPTS and the carboxyl group-containing vinyl monomer in step (2) is 7: (3-5); the using amount of the photoinitiator is 3.5 +/-1.5 percent of the total monomer mass; the alcohol organic solvent is one or more of isopropanol, n-butanol or ethanol.
5. The preparation method according to any one of claims 1 to 4, wherein the molecular weight of the polyvinyl alcohol binder in the step (3) is 16000, and the mass ratio of MXene to polyvinyl alcohol is (1-2): 1; the pore size of the PVDF membrane is preferably 0.22 micron; the loading capacity of the MXene on the membrane is 15mg m-2-30mg m-2(ii) a The spraying amount of the carboxyl siloxane is 1-3mL m-2。
6. The method according to any one of claims 1 to 4, wherein the MXene aqueous dispersion solution prepared in the step (1) is prepared by: adding MAX powder and lithium fluoride (LiF) slowly into a concentrated hydrochloric acid solution, stirring uniformly, etching at room temperature, centrifuging to obtain a multilayer MXene nanosheet, ultrasonically stripping the multilayer MXene nanosheet, and centrifuging to obtain a small-layer MXene aqueous dispersion solution.
7. The method as claimed in any one of claims 1 to 4, wherein the MAX powder in step (1) has a particle size of 200-600 mesh, and the mass ratio of MAX powder to LiF is 1: (1-2); the stripped multilayer MXene is subjected to ultrasonic treatment in ethanol.
8. The method according to any one of claims 1 to 4, wherein the drying temperature in step (3) is 70 to 120 ℃ and the drying time is 1 to 3 hours.
9. An MXene separation membrane produced by the process of any one of claims 1 to 8.
10. Use of the MXene separation membrane of claim 9 for the simultaneous separation of oil and dye.
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