CN118007275A - Preparation method of MOF nanofiber membrane for water treatment - Google Patents
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- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 22
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- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 11
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- YDMVPJZBYSWOOP-UHFFFAOYSA-N 1h-pyrazole-3,5-dicarboxylic acid Chemical compound OC(=O)C=1C=C(C(O)=O)NN=1 YDMVPJZBYSWOOP-UHFFFAOYSA-N 0.000 claims description 3
- JGDITNMASUZKPW-UHFFFAOYSA-K aluminium trichloride hexahydrate Chemical compound O.O.O.O.O.O.Cl[Al](Cl)Cl JGDITNMASUZKPW-UHFFFAOYSA-K 0.000 claims description 3
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- YAGCJGCCZIARMJ-UHFFFAOYSA-N N1C(=NC=C1)C=O.[Zn] Chemical compound N1C(=NC=C1)C=O.[Zn] YAGCJGCCZIARMJ-UHFFFAOYSA-N 0.000 claims description 2
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Abstract
The invention discloses a preparation method of a MOF nanofiber membrane for water treatment, in particular to a preparation method of a MOF-303@PVA nanofiber membrane, and belongs to the field of water treatment material preparation. According to the method, MOF is used as a filler, the MOF is mixed and modified with an environment-friendly water-soluble polymer, and an electrostatic spinning and steam crosslinking method is adopted to prepare the MOF@polymer nanofiber membrane. The active groups on the MOF ligand react with glutaraldehyde and are crosslinked in the three-dimensional network polymer nanofiber. The MOF is stably loaded on the polymer nanofiber membrane, the low dissolution rate of the MOF in water environment is ensured, and the original pore structure and high adsorption performance of the MOF are ensured by utilizing the advantage of large specific surface area of the nanofiber. The method is simple to operate and free from environmental pollution, and solves the problems that pure MOF powder is limited in practical application of water treatment due to the fact that the pure MOF powder is insoluble, poor in processability, brittle, potential safety hazard of dust formation, difficult to separate from aqueous solution and the like; according to the method, the interface structure of the MOF and the polymer matrix is optimized, the advantages of the polymer fiber film such as large specific surface area, excellent pore structure and adsorption performance of the MOF are combined, and the MOF nanofiber film with excellent adsorption performance of heavy metals, dyes and the like is constructed in a cooperative manner.
Description
Technical Field
The invention discloses a preparation method of an MOF nanofiber membrane for water treatment, in particular relates to a preparation method of an MOF-303@PVA nanofiber membrane, and belongs to the field of water treatment material preparation.
Background
The shortage of water resources is the most serious resource problem faced by the 21 st century human beings, and the continuous increase of the contents of heavy metals, dyes and the like in the water quality environment is a key factor causing environmental pollution, especially water pollution. Therefore, the efficient removal of heavy metals, dyes and the like in the water body becomes an effective way for solving the water resource crisis in the 21 st century, and has important significance. In various technologies for removing heavy metals, dyes and the like, the adsorption method has wide application prospect in the field of water treatment due to the advantages of simplicity in operation, low cost, high efficiency and the like.
The metal-organic framework (MOF) material is an emerging porous organic-inorganic hybrid material, and has the advantages of large specific surface area, adjustable porous structure, numerous active sites and the like, thereby having great application potential in the aspect of water treatment. The MOF-303 has classical 1D pore canal, two adjacent ligands can form unique 4N bipyrazole adsorption sites, and the adsorption sites are distributed on the pore canal wall surface of the material instead of the pore canal opening, so that the pore blocking effect caused by adsorption of metal ions, dye macromolecules and the like can be greatly reduced, the MOF-303 has very excellent chemical adsorption and physical adsorption performance, and meanwhile, the MOF-303 has excellent water stability. However, pure MOF powder has many limitations in practical applications in water treatment such as heavy metal adsorption due to its insolubility, poor workability, brittleness, potential safety hazard of dust formation, difficulty in separation from aqueous solutions, and the like. Therefore, it is of great importance to explore MOF composites with good separation properties.
The nanofiber has been widely applied to the fields of national defense, environment, bioengineering, electronics and the like by virtue of excellent properties such as high specific surface area, small size effect, surface effect and the like. The solution electrostatic spinning method is a simple and important method capable of efficiently preparing continuous nanofibers. However, the polymer currently available for electrostatic spinning uses solvents mainly including organic solvents, which are liable to cause certain harm to the environment and human body. Water-soluble electrospun polymer materials containing functional groups such as-COOH, -OH, etc. such as water-soluble polyvinyl alcohol (PVA), polyacrylic acid (PAA), polyvinylpyrrolidone (PVP) have become a trend of development.
The combination of MOF and electrospun nanofibers is prospective in the morphology, structure and chemistry of the final product, opening up new opportunities for efficient water treatment. Based on the problems that the MOF water treatment application process has poor processability, potential safety hazards of dust formation, difficulty in preparing the MOF nanofiber membrane from aqueous solution and the like, the preparation method of the MOF nanofiber membrane is to be adopted, namely, MOF is taken as a filler, the MOF is mixed and modified with an environment-friendly polymer aqueous solution, and the MOF nanofiber membrane is prepared by adopting an electrostatic spinning and steam crosslinking method.
Disclosure of Invention
The invention aims to solve the problems that pure MOF powder has poor processability and potential safety hazard of dust formation in the water treatment application process, is difficult to form in aqueous solution and the like, and provides a method for successfully preparing MOF nanofiber membrane materials for water treatment by adopting simple electrostatic spinning and steam crosslinking.
According to the invention, functional groups such as-COOH, -NH, -CHO and the like in MOF ligands are used pertinently, and are easy to generate chemical crosslinking reaction with functional groups such as-OH, -COOH and the like in polymer matrixes under acidic (or glutaraldehyde-containing) conditions, and MOF is wrapped or partially crosslinked in polymer nanofibers of a three-dimensional network by an electrostatic spinning and steam crosslinking method, so that the MOF@polymer nanofiber membrane is obtained. The method is simple and easy to implement, can ensure the MOF to be stably loaded on the polymer nanofiber membrane, has low dissolution rate, can utilize the large specific surface area of the nanofiber, and ensures the original pore structure and high adsorption performance of the MOF.
The technical scheme of the invention is as follows:
The MOF nanofiber membrane for water treatment consists of MOF and a water-soluble polymer nanofiber membrane, and functional groups such as-COOH, -NH, -CHO and the like in a ligand are easy to chemically react with functional groups such as-OH, -COOH and the like in a polymer matrix under acidic (or glutaraldehyde-containing) conditions, and the MOF is wrapped or partially crosslinked in the polymer nanofiber of a three-dimensional network by an electrostatic spinning and chemical crosslinking method, so that the low dissolution rate and high adsorption performance of the MOF nanofiber membrane under water environment are ensured.
The preparation method of the MOF nanofiber membrane for water treatment specifically comprises the following steps:
Step (1) synthesizing MOF powder material: weighing metal salt and ligand, adding solvent to dissolve to obtain solution, heating the solution to react for a period of time, centrifuging, washing and drying to obtain MOF powder;
The ligand of the MOF contains functional groups such as-COOH, -NH, -CHO and the like, such as one or more of MOF-303, uiO-66-NH 2, ZIF-90 and the like. The MOF is preferably MOF-303.
Weighing a certain mass of water-soluble polymer, adding the water into the water, dissolving the water at a certain temperature to obtain a polymer homogeneous aqueous solution, adding a certain mass of MOF obtained in the step (1) into the polymer aqueous solution, and fully and uniformly stirring the mixture at room temperature to obtain a homogeneous MOF/polymer spinning solution; injecting a spinning solution into a 5 mL spinning needle tube for electrostatic spinning to obtain an MOF/polymer nanofiber membrane;
The polymer is one or more of water-soluble electrospun common polymer raw materials containing functional groups such as-COOH, -OH and the like, such as polyvinyl alcohol (PVA), polyethylene oxide (PEO), polyacrylic acid (PAA), polyvinylpyrrolidone (PVP) and the like. The polymer is preferably polyvinyl alcohol (PVA, model 1788).
The concentration of the polymer aqueous solution is 5% -50%, the dissolution temperature is 25% -100 ℃, and the dissolution time is 3-12 hours; fully stirring for 6-24 hours; the MOF addition amount is 0% -5%.
The electrostatic spinning conditions are as follows: 12-25 kV; spinning rate: 0.0005-0.15 mm/s; receiving distance: 7-20 cm.
And (3) placing the MOF/polymer nanofiber membrane obtained in the step (2) into a steam crosslinking device containing glutaraldehyde/glacial acetic acid for crosslinking to obtain the MOF@polymer nanofiber membrane.
The glutaraldehyde: the volume ratio of glacial acetic acid is 10:0.01-2:1, and the crosslinking time is 0.05-12 h.
For the preferred material PVA, MOF-303, step (1) above is accomplished by the following procedure:
Firstly, 5.2 g of aluminum trichloride hexahydrate (AlCl 3·6H2 O) and 1.75 g of 3, 5-pyrazoledicarboxylic acid (H 2 PDC) are weighed and poured into a 500 mL round-bottom flask, and 360 mL of deionized water is added to dissolve the materials to obtain a solution A; 2.6 g sodium hydroxide (NaOH) is weighed and dissolved in 30 mL water to prepare a NaOH solution (2.17M), the NaOH solution is slowly added into the solution A for multiple times to obtain a solution B, and the solution B is heated in an oil bath at 100 ℃ to carry out reflux reaction for 24 h. After the completion of the reaction system, white solid powder was obtained by centrifugation. The resulting solid powder was washed 3 times with deionized water and methanol, respectively. Finally, after drying the sample in a vacuum oven at 140 ℃ for 24h, MOF-303 powder was obtained.
The step (2) is realized through the following operation steps:
Weighing 5-20 g of polyvinyl alcohol (PVA) solid, adding 80-95 g of deionized water, mixing, and dissolving at 80-100 ℃ for 3-6 hours to obtain a PVA aqueous solution with the mass fraction of 5-20%. And adding 0-5 g of MOF-303 into the PVA aqueous solution, and fully mixing and stirring at room temperature for 12-24 hours to obtain a homogeneous MOF-303/PVA spinning solution. Injecting spinning solution into a5 mL spinning needle tube, and setting voltage: 15-25 kV; spinning rate: 0.0005 to 0.015mm/s; receiving distance: and 7-20 cm, and carrying out electrostatic spinning to obtain the MOF-303/PVA nanofiber membrane.
The step (3) is realized through the following operation steps:
Placing the MOF-303/PVA nanofiber prepared in the step (2) into a fiber containing glutaraldehyde: and (3) in a room-temperature steam crosslinking reactor, wherein the mixed solution with the glacial acetic acid volume ratio of 10:0.01-2:1 is used as a crosslinking agent, and the reaction is carried out for 0.05-12 h at room temperature, so that the MOF-303@PVA nanofiber membrane is finally obtained.
The MOF nanofiber membrane consists of MOF-303 and a polyvinyl alcohol (PVA) nanofiber membrane, imino groups on ligands in the MOF-303 react with glutaraldehyde to be crosslinked in PVA nanofibers of a three-dimensional network, and the MOF is stably loaded on the polymer nanofiber membrane to ensure low dissolution rate under water environment, so that the MOF nanofiber membrane can be used in adsorption separation processes of heavy metals, dyes and the like.
The beneficial technical effects of the application
According to the MOF nanofiber membrane disclosed by the invention, the MOF is wrapped or partially crosslinked in the polymer nanofiber of a three-dimensional network by utilizing the functional groups of-COOH, -NH, -CHO and the like in the ligand and the functional groups of-OH, -COOH and the like in the polymer matrix to easily react under the acidic (or glutaraldehyde-containing) condition, and the MOF is wrapped or partially crosslinked in the polymer nanofiber of the three-dimensional network by an electrostatic spinning and chemical crosslinking method, so that the MOF@polymer nanofiber membrane is obtained.
Furthermore, the invention solves the problems of insoluble property, poor processability, brittleness, potential safety hazard of dust formation, difficulty in separation from aqueous solution and the like of the pure MOF powder, can ensure that MOF is stably loaded on a polymer nanofiber membrane, has low dissolution rate, can utilize large specific surface area of nanofiber and ensures the original pore structure, chemical stability and adsorption performance of MOF.
Furthermore, the preparation method has the advantages of mild reaction conditions, environmental protection, simple process, easy preparation, easy processing and the like, and is suitable for industrial mass production.
Drawings
FIG. 1 is an optical view showing the dissolution state of the PVA nanofiber membrane (a) before crosslinking and the PVA nanofiber crosslinked membrane (b) after crosslinking in water in example 1.
FIG. 2 is a graph showing the effect of the PVA nanofiber crosslinked film (a) of example 1 and the MOF@PVA nanofiber film (b) of example 4 on adsorption of heavy metals.
FIG. 3 is a graph showing the effect of adsorbing dye by the PVA nanofiber crosslinked film (a) of example 1 and the MOF@PVA nanofiber film (b) of example 4.
Fig. 4 is a schematic diagram.
Detailed Description
The technical solution of the present application will be further described below by means of several specific embodiments in conjunction with the embodiments shown in fig. 1 to 4, but the present application is not limited thereto, and modifications and implementations are included in the technical scope of the present application without departing from the content and scope of the present application.
Example 1
The preparation method of the MOF nanofiber membrane for water treatment comprises the following steps of:
(1) Weighing a certain mass of water-soluble polymer, adding the water into water, and dissolving the water at a certain temperature to obtain a polymer homogeneous spinning solution; injecting a spinning solution into a 5mL spinning needle tube for electrostatic spinning to obtain a polymer nanofiber membrane, wherein the specific operation steps are as follows:
10 g solid of polyvinyl alcohol (PVA, model 1788) is weighed, 90g of deionized water is added for mixing, and 4: 4h of PVA is dissolved at 90 ℃ to obtain 10% PVA aqueous solution by mass fraction. Injecting spinning solution into a 5mL spinning needle tube, and setting voltage: 18 A kV; spinning rate: 0.001mm/s; reception distance: 12 cm, carrying out electrostatic spinning to obtain the PVA nanofiber membrane.
(2) Placing the PVA nanofiber membrane obtained in the step (1) into a steam crosslinking device containing glutaraldehyde/glacial acetic acid for crosslinking to obtain the PVA nanofiber crosslinked membrane, wherein the specific operation steps are as follows:
Placing the PVA nanofiber prepared in the step (1) into a fiber containing glutaraldehyde: the volume ratio of glacial acetic acid is 9: and (3) in a room-temperature steam crosslinking reactor taking the mixed solution of the step (1) as a crosslinking agent, reacting at room temperature for 1h to finally obtain the PVA nanofiber crosslinked film.
And (3) respectively placing the PVA nanofiber membranes prepared in the step (1) and the step (2) in water environment. The PVA nanofiber membrane before crosslinking and the PVA nanofiber crosslinked membrane after crosslinking obtained above were observed in a dissolved state, and the obtained optical pattern was shown in FIG. 1.
FIG. 1 shows that PVA nanofibers prior to crosslinking are unstable in water, are very soluble in water, and cannot maintain their structural integrity (FIGS. 1 a-b); while PVA nanofibers crosslinked with steam can remain structurally stable in water (FIGS. 1 c-d).
Example 2
The preparation method of the MOF nanofiber membrane for water treatment comprises the following steps of:
(1) Synthesizing MOF powder material: weighing metal salt and ligand, adding solvent to dissolve to obtain solution, heating the solution to react for a period of time, centrifuging, washing and drying to obtain MOF powder, wherein the specific operation steps are as follows:
Firstly, 5.2 g of aluminum trichloride hexahydrate (AlCl 3·6H2 O) and 1.75 g of 3, 5-pyrazoledicarboxylic acid (H 2 PDC) are weighed and poured into a 500 mL round-bottom flask, and 360 mL of deionized water is added to dissolve the materials to obtain a solution A; 2.6 g sodium hydroxide (NaOH) is weighed and dissolved in 30 mL water to prepare a NaOH solution (2.17M), naOH is slowly added into the solution A for multiple times to obtain a solution B, and the solution B is heated in an oil bath at 100 ℃ to carry out reflux reaction for 24 h. After the completion of the reaction system, white solid powder was obtained by centrifugation. The resulting solid powder was washed 3 times with deionized water and methanol, respectively. Finally, after drying the sample in a vacuum oven at 140 ℃ for 24h, MOF-303 powder was obtained.
(2) Weighing a certain mass of water-soluble polymer, adding the water into the water, dissolving the water at a certain temperature to obtain a polymer homogeneous aqueous solution, adding a certain mass of MOF obtained in the step (1) into the polymer aqueous solution, and fully and uniformly stirring the mixture at room temperature to obtain a homogeneous MOF/polymer spinning solution; injecting spinning solution into a5 mL spinning needle tube for electrostatic spinning to obtain the MOF/polymer nanofiber membrane, wherein the specific operation steps are as follows:
10 g polyvinyl alcohol (PVA) solids are weighed, 90 g deionized water is added for mixing, and 4h is dissolved at 90 ℃ to obtain a PVA aqueous solution with the mass fraction of 10%. Adding 0.3 g MOF-303 into PVA water solution, mixing and stirring thoroughly at room temperature for 12-24h to obtain homogeneous MOF-303/PVA spinning solution. Injecting spinning solution into a5 mL spinning needle tube, and setting voltage: 18 A kV; spinning rate: 0.001 mm/s; receiving distance: 12 cm, carrying out electrostatic spinning to obtain the MOF-303/PVA nanofiber membrane.
(3) And (3) placing the MOF-303/PVA nanofiber membrane obtained in the step (2) in a steam crosslinking device containing glutaraldehyde/glacial acetic acid for crosslinking to obtain the MOF@PVA nanofiber membrane, wherein the specific steps are the same as the step (2) in the example 1.
Example 3
The preparation method of the MOF nanofiber membrane for water treatment comprises the following steps of:
(1) Synthesizing MOF powder material: weighing metal salt and ligand, adding solvent to dissolve to obtain solution, heating the solution to react for a period of time, centrifuging, washing, and drying to obtain MOF powder, wherein the specific steps are the same as in step (1) of example 2.
(2) Weighing a certain mass of water-soluble polymer, adding the water into the water, dissolving the water at a certain temperature to obtain a polymer homogeneous aqueous solution, adding a certain mass of MOF obtained in the step (1) into the polymer aqueous solution, and fully and uniformly stirring the mixture at room temperature to obtain a homogeneous MOF/polymer spinning solution; and (3) injecting a spinning solution into a 5mL spinning needle tube for electrostatic spinning to obtain the MOF/polymer nanofiber membrane, wherein the specific steps are the same as the step (2) of the example 2, except that the adding amount of the MOF-303 is 0.8 g.
(3) And (3) placing the MOF/PVA nanofiber membrane obtained in the step (2) in a steam crosslinking device containing glutaraldehyde/glacial acetic acid for crosslinking to obtain the MOF@PVA nanofiber membrane, wherein the specific steps are the same as those in the step (2) of the example 1.
Example 4
The preparation method of the MOF nanofiber membrane for water treatment comprises the following steps of:
(1) Synthesizing MOF powder material: weighing metal salt and ligand, adding solvent to dissolve to obtain solution, heating the solution to react for a period of time, centrifuging, washing, and drying to obtain MOF powder, wherein the specific steps are the same as in step (1) of example 2.
(2) Weighing a certain mass of water-soluble polymer, adding the water into the water, dissolving the water at a certain temperature to obtain a polymer homogeneous aqueous solution, adding a certain mass of MOF obtained in the step (1) into the polymer aqueous solution, and fully and uniformly stirring the mixture at room temperature to obtain a homogeneous MOF/polymer spinning solution; and (3) injecting a spinning solution into a 5mL spinning needle tube for electrostatic spinning to obtain the MOF/PVA nanofiber membrane, wherein the specific step is the same as the step (2) of the embodiment 2, except that the adding amount of the MOF-303 is 1.5 g.
(3) And (3) placing the MOF/polymer nanofiber membrane obtained in the step (2) in a steam crosslinking device containing glutaraldehyde/glacial acetic acid for crosslinking to obtain the MOF@PVA nanofiber membrane, wherein the specific steps are the same as those in the step (2) of the example 1.
A Cu 2+ ion solution with a concentration of 100 ppm was prepared, and the PVA nanofiber crosslinked film in example 1 and the mof@pva nanofiber film in example 4 were used as adsorption films, and the Cu 2+ ion solution was adsorbed at 25 ℃ and pH of 7, respectively, for testing. And observing the heavy metal adsorption effect of the PVA nanofiber crosslinked film and the MOF@PVA nanofiber film, wherein the obtained optical diagram is shown in figure 2.
FIG. 2 shows that PVA nanofiber crosslinked membranes have poor ability to adsorb heavy metals; and the MOF@PVA nanofiber membrane has strong heavy metal adsorption capacity.
Congo red dye solution with concentration of 100 ppm is prepared, and the PVA nanofiber crosslinked film in example 1 and the MOF@PVA nanofiber film in example 4 are used as adsorption films, and are respectively subjected to dye adsorption test at 25 ℃ and pH of 7. The dye adsorption effect of the PVA nanofiber crosslinked film and the MOF@PVA nanofiber film was observed, and the obtained optical diagram is shown in FIG. 3.
FIG. 3 shows that PVA nanofiber crosslinked membranes have poor dye adsorption capacity; and the MOF@PVA nanofiber membrane has stronger dye adsorption capacity.
The above detailed description is only for explaining the technical solution of the present invention in detail, the present invention is not limited to the above examples, and it should be understood that those skilled in the art should all modifications and substitutions based on the above principles and spirit are within the scope of the present invention.
Claims (10)
1. The preparation method of the MOF nanofiber membrane for water treatment is characterized by comprising the following steps of:
Step (1) synthesizing MOF powder material: weighing metal salt and ligand, adding solvent to dissolve to obtain solution, heating the solution to react for a period of time, centrifuging, washing and drying to obtain MOF powder;
Weighing a certain mass of water-soluble polymer, adding the water into the water, dissolving the water at a certain temperature to obtain a polymer homogeneous aqueous solution, adding a certain mass of MOF obtained in the step (1) into the polymer aqueous solution, and fully and uniformly stirring the mixture at room temperature to obtain a homogeneous MOF/polymer spinning solution; injecting a spinning solution into a 5 mL spinning needle tube for electrostatic spinning to obtain an MOF/polymer nanofiber membrane;
And (3) placing the MOF/polymer nanofiber membrane obtained in the step (2) into a steam crosslinking device containing glutaraldehyde/glacial acetic acid for crosslinking to obtain the MOF@polymer nanofiber membrane.
2. The method for preparing the MOF nanofiber membrane for water treatment according to claim 1, wherein the method comprises the following steps: the ligand in MOF contains functional groups such as-COOH, -NH, -CHO, etc., such as one or more of MOF-303, uiO-66-NH 2, ZIF-90, etc. The MOF is preferably MOF-303.
3. The method for preparing the MOF nanofiber membrane for water treatment according to claim 1, wherein the method comprises the following steps: the polymer in the step (2) is one or more of polyvinyl alcohol PVA, polyethylene oxide PEO, polyacrylic acid PAA, polyvinylpyrrolidone PVP, water-soluble electrostatic spinning common high molecular polymer raw materials containing functional groups such as-COOH, -OH and the like; the polymer is preferably polyvinyl alcohol.
4. The method for preparing the MOF nanofiber membrane for water treatment according to claim 1, wherein the method comprises the following steps: the concentration of the polymer aqueous solution in the step (2) is 5% -50%, the dissolution temperature is 25% -100 ℃, and the dissolution time is 3-12 hours; fully stirring for 6-24 hours; the MOF addition amount is 0% -5%.
5. The method for preparing the MOF nanofiber membrane for water treatment according to claim 1, wherein the method comprises the following steps: the electrostatic spinning condition in the step (2) is as follows: 12-25 kV; spinning rate: 0.0005-0.15 mm/s; receiving distance: 7-20 cm.
6. The method for preparing the MOF nanofiber membrane for water treatment according to claim 1, wherein the method comprises the following steps: glutaraldehyde in step (3): the volume ratio of glacial acetic acid is 10:0.01-2:1, and the crosslinking time is 0.05-12 h.
7. A process for the preparation of a MOF nanofiber membrane for water treatment according to any of claims 1-6, characterized in that for the preferred material MOF-303, step (1) is achieved by the following operative steps:
Firstly, 5.2 g aluminum trichloride hexahydrate AlCl 3·6H2 O and 1.75 g of 3, 5-pyrazole dicarboxylic acid H 2 PDC are weighed and poured into a 500 mL round bottom flask, and 360 mL deionized water is added to dissolve the materials to obtain a solution A; 2.6 g sodium hydroxide NaOH is weighed and dissolved in 30 mL water to prepare NaOH solution 2.17 and M, naOH is slowly added into solution A for multiple times to obtain solution B, and the solution B is heated in an oil bath at 100 ℃ to carry out reflux reaction for 24. 24 h. After the reaction system is finished, white solid powder is obtained through centrifugation; washing the obtained solid powder with deionized water and methanol for 3 times respectively; finally, after drying the sample in a vacuum oven at 140 ℃ for 24 h, MOF-303 powder was obtained.
8. The method for preparing a MOF nanofiber membrane for water treatment according to claims 1 to 6, characterized in that for the preferred polymer material PVA, step (2) is achieved by the following operation steps:
Weighing 5-20 g of polyvinyl alcohol (PVA) solid, adding 80-95 g of deionized water, mixing, and dissolving at 80-100 ℃ for 3-12 h to obtain a PVA aqueous solution with the mass fraction of 5-20%. Adding 0-5 g of MOF-303 into the PVA water solution, and fully mixing and stirring at room temperature for 12-24 hours to obtain a homogeneous MOF-303/PVA spinning solution; injecting spinning solution into a 5mL spinning needle tube, and setting voltage: 15-25 kV; spinning rate: 0.0005-0.015 mm/s; receiving distance: and 7-20 cm, and carrying out electrostatic spinning to obtain the MOF-303/PVA nanofiber membrane.
9. The method for preparing a MOF nanofiber membrane for water treatment according to claims 1 to 6, wherein the step (3) is realized by the following steps:
Placing the MOF-303/PVA nanofiber prepared in the step (2) into a fiber containing glutaraldehyde: crosslinking the mixed solution with the glacial acetic acid volume ratio of 10:0.01-2:1 serving as a crosslinking agent in a room-temperature steam crosslinking reactor at room temperature for 0.05-12 h to finally obtain the MOF-303@PVA nanofiber membrane;
The MOF nanofiber membrane consists of MOF-303 and a polyvinyl alcohol PVA nanofiber membrane, the MOF is wrapped or partially crosslinked in the PVA nanofiber of the three-dimensional network, and the MOF is stably loaded on the polymer nanofiber membrane, so that the low dissolution rate under water environment is ensured.
10. The preparation method of the MOF nanofiber membrane for water treatment according to any one of claims 1 to 9, which is characterized in that the MOF nanofiber membrane is used in the water treatment fields such as heavy metal adsorption and dye adsorption.
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