Functionalized MOFs / porous fiber membrane as well as preparation method and application thereof

Abstract

The invention belongs to the technical field of photocatalytic antibacterial nano materials, and particularly relates to a functional MOFs / porous fiber membrane and a preparation method and application thereof.The functional MOFs / porous fiber membrane is prepared by taking MOFs and a fiber membrane as raw materials and adopting crosslinking of metal active sites, modified groups and active groups in the porous fiber membrane, so that the MOFs grow into the porous fiber membrane in situ, and the functional MOFs / porous fiber membrane is prepared. The functionalized MOFs / porous fiber membrane is obtained. Based on the characteristic of large specific surface area of the fiber membrane and the MOFs, the MOFs / porous fiber membrane can adsorb bacteria and sterilize at the same time, has a better antibacterial function, and also has an excellent function of catalytically degrading antibiotics. The problems that powdery MOFs are easy to agglomerate, difficult to recycle, low in repeated utilization rate and the like are solved, the fiber membrane is endowed with multiple functions of antibiosis, adsorption, photocatalysis and the like, and the application prospect is wide.

Description

Technical Field

[0001] The present invention belongs to the technical field of photocatalytic antibacterial nanomaterials, and specifically relates to a functionalized MOFs / porous fiber membrane and a preparation method thereof, and also relates to the application of the MOFs / porous fiber membrane in antibacterial and photocatalytic degradation of antibiotics. Background Art

[0002] At present, a large amount of antibiotic wastewater enters the environment every year. Organisms affected by antibiotics in the environment may be enriched in the human body through the food chain. The first to be affected is the microbial population in the human intestine. Changes in the proportion and activity of the bacterial population can easily cause gastrointestinal diseases such as diarrhea, colitis, etc., and trigger a series of pathogenic bacteria infections.

[0003] The research and development of antibacterial materials has also become a hot topic of current research. MOFs materials have the advantages of highly controllable structure, high specific surface area and adjustable pore size, and are widely used in adsorption, catalysis and antibacterial fields. However, since powdered MOFs are easy to agglomerate during adsorption and degradation, their antibacterial and catalytic effects are limited. In addition, MOFs particles are difficult to recycle after use, and the reuse rate is low. Therefore, how to improve its antibacterial and catalytic properties while improving its recycling rate is an urgent problem that needs to be solved. Summary of the invention

[0004] In view of the problem that MOFs materials are easy to agglomerate in their applications, resulting in limited antibacterial and catalytic effects and difficulty in recycling, the purpose of the present invention is to provide a functional MOFs / porous fiber membrane and a preparation method thereof. The fiber membrane is made porous and MOFs are synthesized in situ on the fiber membrane to obtain a MOFs / porous fiber membrane composite material. This not only solves the problem that powdered MOFs are easy to agglomerate, resulting in poor antibacterial and catalytic effects, but is also easy to recycle and reuse and has good cyclic stability.

[0005] Based on the above purpose, the technical solution adopted by the present invention is as follows:

[0006] In a first aspect, the present invention provides a functionalized MOFs / porous fiber membrane, wherein the MOFs / porous fiber membrane is composed of MOFs synthesized in situ on a porous fiber membrane; the content of MOFs in the MOFs / porous fiber membrane is 16 wt % to 25 wt %.

[0007] Based on the fact that the fiber membrane and MOFs have a large specific surface area, the MOFs / porous fiber membrane composite material of the present invention can kill bacteria while adsorbing bacteria, and has better antibacterial function. In addition, the MOFs / porous fiber membrane of the present invention also has excellent photocatalytic degradation of antibiotics. Since MOFs and the fiber membrane are in situ cross-linked, the fiber membrane has better structural stability and solubility resistance, the antibacterial active ingredients are not easy to precipitate, the antibacterial activity is longer, and the photocatalytic performance is more stable and lasting, which solves the problem of poor antibacterial and catalytic effects caused by the easy agglomeration of powdered MOFs.

[0008] In addition, the MOFs / porous fiber membrane of the present invention can be recycled and easily recovered, and has good cycle stability, thus solving the problem that the existing MOFs particles are difficult to recover and reuse after use.

[0009] Preferably, MOFs are UIO-66, MIL-101, HKUST-1, ZIF-8, ZIF-67, UIO-66-NH 2 At least one of .

[0010] Preferably, the fiber membrane is at least one of filter paper, cotton, wool, soybean protein fiber and polyvinyl chloride fiber.

[0011] In a second aspect, the present invention provides a method for preparing the above-mentioned functionalized MOFs / porous fiber membrane, comprising the following steps:

[0012] S1: soaking the fiber membrane in an organic solvent, adding alkali solution for reaction, then adding sodium chloroacetate to the reaction system for reaction, and reacting at a certain temperature for 3 to 5 hours to obtain a porous fiber membrane;

[0013] S2: Add the porous fiber membrane to a mixed solution of an organic ligand solution and a metal salt solution, and then continue to add the organic ligand solution and the metal salt solution to immerse the porous fiber membrane, and react at 30 to 50° C. for 5 to 20 hours to obtain a MOFs / porous fiber membrane.

[0014] The present invention uses MOFs and fiber membranes as raw materials, and adopts metal active sites and modified groups to cross-link with active groups in the fiber membranes, so that MOFs are successfully loaded onto the fiber membranes to obtain functionalized MOFs / porous fiber membranes.

[0015] In the preparation process, the present invention uses the alkalized fiber membrane to react with sodium chloroacetate under specific conditions to carry out an etherification reaction, and some hydroxyl groups on the cellulose molecular chain are replaced by carboxymethyl groups (-CH 2-COOH) is replaced to form carboxymethyl cellulose. Without the effect of sodium chloroacetate, there are only hydroxyl groups on the fiber molecular chain. The binding force between hydroxyl groups and MOFs is relatively weak, the binding is not firm, and it is easy to cause uneven dispersion of MOFs on the fiber surface. However, there are a large number of evenly distributed carboxymethyl groups on the surface of the carboxymethylated fiber, which makes MOFs and the fiber membrane firmly bonded through chemical bonds, thus solving the problem of weak binding and poor dispersion of MOFs in the fiber membrane. The firm binding of MOFs to the fiber membrane further improves its antibacterial activity and photocatalytic performance.

[0016] The present invention adopts the method of first adding a mixed solution of an organic ligand solution and a metal salt solution to a porous fiber membrane, uniformly wetting the porous fiber membrane, and then respectively adding equal volumes of an organic ligand solution and a metal salt solution to completely immerse the porous fiber membrane. The step-by-step operation is more conducive to the in-situ synthesis of MOFs on the porous fiber membrane, and makes the MOFs more evenly dispersed on the porous fiber membrane.

[0017] Preferably, the concentration of sodium chloroacetate in the reaction system of step S1 is 30-60 g / L.

[0018] The appropriate concentration of sodium chloroacetate in the reaction system is crucial to the porosity of the fiber membrane. When the concentration of sodium chloroacetate in the reaction system is lower than 30 g / L, it is not conducive to the carboxymethylation of the fiber molecular chains in the fiber membrane, and thus is not conducive to the in situ synthesis of MOFs in the fiber membrane; when the concentration of sodium chloroacetate in the reaction system is higher than 60 g / L, the water absorption of the fiber membrane will be greatly enhanced, resulting in excessive water absorption of the fiber membrane, which not only wastes reagents but also is not conducive to the subsequent reaction.

[0019] Preferably, the reaction temperature after adding sodium chloroacetate in step S1 is 35-50°C.

[0020] When using sodium chloroacetate to make the fiber membrane porous, the reaction temperature is more important. When the temperature is lower than 35°C, the solubility and uniform dispersion of sodium chloroacetate in the reaction system are poor, which is not conducive to the uniform porous treatment of the fiber membrane; when the reaction temperature is higher than 50°C, the fiber structure in the fiber membrane will be destroyed, resulting in sample preparation failure.

[0021] Preferably, the volume ratio of the organic ligand solution to the metal salt solution in the mixed solution in step S2 is 1:1; the volume ratio of the organic ligand solution continued to be added in step S2 to the metal salt solution is 1:1; the concentration of the organic ligand in the organic ligand solution is 2-5 g / L; the concentration of the metal salt in the metal salt solution is 3-13 g / L.

[0022] Preferably, the organic solvent is an isopropanol aqueous solution, and the volume fraction of isopropanol in the isopropanol aqueous solution is 80% to 85%.

[0023] Preferably, the alkali solution is sodium hydroxide or potassium hydroxide solution, and the concentration of the alkali solution is 0.02-0.1 mol / L.

[0024] Preferably, the organic ligand solution is prepared by dissolving the organic ligand in a dispersant, and the metal salt solution is prepared by dissolving the metal salt in a dispersant, and the dispersant is at least one of methanol, ethanol, acetone, chloroform and N,N-dimethylformamide.

[0025] In a third aspect, the present invention provides a method for regenerating the above-mentioned functionalized MOFs / porous fiber membrane, comprising the following steps: treating the MOFs / porous fiber membrane again according to the above-mentioned step S2 to achieve the regeneration of the MOFs / porous fiber membrane.

[0026] The regeneration method of the MOFs / porous fiber membrane of the present invention is simple, and the regenerated MOFs / porous fiber membrane still has good antibacterial properties and antibiotic degradation properties. After being regenerated 5 times, it still shows excellent antibiotic degradation performance, and the regeneration cycle stability is better.

[0027] In a fourth aspect, the present invention provides an application of the above-mentioned functionalized MOFs / porous fiber membrane in antibacterial applications, wherein the MOFs / porous fiber membrane has an inhibitory effect on Escherichia coli, Staphylococcus aureus, and Aspergillus niger.

[0028] It is found through experiments that the MOFs / porous fiber membrane prepared by the present invention has excellent antibacterial properties against Escherichia coli, Staphylococcus aureus and Aspergillus niger.

[0029] In a fifth aspect, the present invention provides the use of the above-mentioned functionalized MOFs / porous fiber membrane in the photocatalytic degradation of antibiotics.

[0030] Preferably, the antibiotic comprises cephalexin.

[0031] It was found through experiments that the MOFs / porous fiber membrane of the present invention has excellent catalytic degradation performance for the antibiotic cephalexin. Only 0.7 g of the product can degrade 100% of the antibiotic in 100 mL 5 mg / L cephalexin aqueous solution within 4 hours.

[0032] Compared with the prior art, the present invention has the following beneficial effects:

[0033] The present invention further treats the alkalinized fiber membrane with sodium chloroacetate to make it porous, so that the porous fiber membrane is mixed with a MOFs precursor solution for reaction, thereby realizing the in-situ synthesis of MOFs on the porous fiber membrane, increasing the loading amount of MOFs materials on the porous fiber membrane, and enhancing the bonding strength of MOFs and the porous fiber membrane. The present invention loads MOFs on the porous fiber membrane in situ, which not only solves the problems of easy agglomeration, difficult recycling, and low reuse rate of powdered MOFs, but also gives the fiber membrane multiple functions such as antibacterial, adsorption, and photocatalysis, and has broad application prospects. At the same time, the present invention has the advantages of low energy consumption, simple equipment, convenient operation, and convenience for industrial production. BRIEF DESCRIPTION OF THE DRAWINGS

[0034] Figure 1 This is a sample picture of the MOFs / porous fiber membrane material of Example 3;

[0035] Figure 2 Electron microscope images of fiber membrane, porous fiber membrane and MOFs / porous fiber membrane;

[0036] Figure 3 The inhibition zone diagrams of fiber membrane, porous fiber membrane and MOFs / porous fiber membrane;

[0037] Figure 4 It is the electron microscope image of comparative example 2;

[0038] Figure 5 This is an electron microscope image of MOFs / porous fiber membrane. DETAILED DESCRIPTION

[0039] In order to better illustrate the purpose, technical scheme and advantages of the present invention, the present invention will be further described below in conjunction with specific embodiments. It should be understood by those skilled in the art that the specific embodiments described herein are only used to explain the present invention and are not intended to limit the present invention. The test methods used in the examples are conventional methods unless otherwise specified; the materials, reagents, etc. used can be obtained from commercial sources unless otherwise specified.

[0040] The metal salts and organic ligands used in the examples of the present invention were purchased from commercial reagent companies such as Shanghai MacLean Biochemical Co., Ltd., Sinopharm Reagent Co., Ltd., and Shanghai Bid Pharmaceutical Co., Ltd.

[0041] Example 1

[0042] In this embodiment, cotton is used as a fiber source to prepare a functional MOFs / porous fiber membrane, and the preparation method thereof includes the following steps:

[0043] (1) 0.35 g of cotton was soaked in 100 mL of water / isopropanol (1 / 4, v / v) solution, and 10 mL of 0.0625 mol / L sodium hydroxide aqueous solution was added under shaking conditions. After reacting for 1 h, 4 g of sodium chloroacetate was added, and the concentration of sodium chloroacetate in the reaction system was 40 g / L. The reaction was shaken at 50 ° C for 3 h to obtain a porous fiber membrane;

[0044] (2) dissolving 0.5 g of trimesic acid in 250 mL of N,N-dimethylformamide to obtain a 2 g / L trimesic acid solution; dissolving 0.9 g of copper nitrate in 250 mL of N,N-dimethylformamide / ethanol solution (v / v=1 / 1) to obtain a 3.6 g / L copper nitrate solution;

[0045] (3) Take 20 mL of trimesic acid solution and add it to 20 mL of copper nitrate solution to obtain a mixed solution of trimesic acid solution and copper nitrate solution, add the porous fiber membrane prepared in step (1) to the mixed solution, and react for 30 minutes. Then, continue to add 60 mL of trimesic acid solution and 60 mL of copper nitrate solution simultaneously. After fully reacting at 50°C for 12 hours, wash and dry the fiber membrane with methanol to obtain MOFs / porous fiber membrane, denoted as HKUST-1 / CMWP, and the content of MOFs in the MOFs / porous fiber membrane is 19wt%.

[0046] Example 2

[0047] In this embodiment, wool is used as a fiber source to prepare a functional MOFs / porous fiber membrane, and the preparation method includes the following steps:

[0048] (1) 0.35 g of wool was soaked in 100 mL of water / isopropanol (1 / 4, v / v) solution, and 10 mL of 0.0625 mol / L sodium hydroxide aqueous solution was added under oscillation. After reacting for 1 h, 5 g of sodium chloroacetate was added, and the concentration of sodium chloroacetate in the reaction system was 50 g / L. The reaction was oscillated at 50 ° C for 4 h to obtain a porous fiber membrane;

[0049] (2) dissolving 1.2 g of dimethylimidazole in 250 mL of N,N-dimethylformamide solution to obtain a 4.8 g / L dimethylimidazole solution; dissolving 2.2 g of zinc nitrate in 250 mL of N,N-dimethylformamide solution to obtain a 8.8 g / L zinc nitrate solution;

[0050] (3) Add 20 mL of dimethylimidazole solution to 20 mL of zinc nitrate solution to obtain a mixed solution of dimethylimidazole and zinc nitrate, add the porous fiber membrane prepared in step (1) to the mixed solution, and react for 30 min. Then, continue to add 60 mL of 2-methylimidazole solution and 60 mL of zinc nitrate solution simultaneously, and react at 30° C. for 10 h, wash the fiber membrane with methanol and then dry it to obtain MOFs / porous fiber membrane, recorded as ZIF-8 / CMWP, and the content of MOFs in the MOFs / porous fiber membrane is 23 wt%.

[0051] Example 3

[0052] In this embodiment, filter paper is used as a fiber source to prepare a functional MOFs / porous fiber membrane, and the preparation method includes the following steps:

[0053] (1) Soak 0.35 g of filter paper in 100 mL of water / isopropanol (1 / 4, v / v) solution, and add 10 mL of 0.0625 mol / L sodium hydroxide aqueous solution under shaking conditions. After reacting for 1 h, add 6 g of sodium chloroacetate, and the concentration of sodium chloroacetate in the reaction system is 60 g / L. Oscillate at 50 ° C for 4 h to obtain a porous fiber membrane;

[0054] (2) dissolving 0.5 g of dimethylimidazole in 100 mL of methanol solution to obtain a 5 g / L dimethylimidazole solution; dissolving 1.2 g of cobalt nitrate in 100 mL of methanol solution to obtain a 12 g / L cobalt nitrate solution;

[0055] (3) Add 20 mL of dimethylimidazole solution to 20 mL of cobalt nitrate solution to obtain a mixed solution of dimethylimidazole and cobalt nitrate, add the porous fiber membrane prepared in step (1) to the mixed solution, and react for 30 minutes. Then, continue to add 60 mL of 2-methylimidazole solution and 60 mL of cobalt nitrate solution simultaneously. After fully reacting at 40°C for 8 hours, wash the fiber membrane with methanol and dry it to obtain a MOFs / porous fiber membrane, which is recorded as ZIF-67 / CMWP. The content of MOFs in the MOFs / porous fiber membrane is 24 wt%.

[0056] The actual photos of MOFs / porous fiber membrane prepared in this example are as follows: Figure 1 shown.

[0057] Comparative Example 1

[0058] 0.35 g of filter paper was soaked in 100 mL of water / isopropanol (1 / 4, v / v) solution, and 10 mL of 0.0625 mol / L sodium hydroxide aqueous solution was added under shaking conditions. After reacting for 1 h, 4 g of sodium chloroacetate was added and shaken at 50 ° C for 3 h to obtain a porous fiber membrane.

[0059] Comparative Example 2

[0060] The only difference between this comparative example and Example 3 is that in step (1) of this comparative example, sodium chloroacetate is not added to the reaction system, and the remaining parts not mentioned are the same as those of Example 3.

[0061] Performance Testing

[0062] 1. Morphology test

[0063] The fiber membrane (filter paper) without any treatment was used as a blank control, wherein the electron microscope photos of the blank control fiber membrane, the porous fiber membrane prepared in Comparative Example 1, and the MOFs / porous fiber membranes prepared in Examples 1 to 3 are as follows: Figure 2 As shown, Figure 2 a and Figure 2 b are the surface electron microscope images of the fiber membrane (blank control) and the porous fiber membrane (Comparative Example 1), respectively. It can be seen from the figures that the surfaces of the fiber membrane (blank control) and the porous fiber membrane (Comparative Example 1) are relatively smooth.

[0064] When MOFs are grown in situ on porous fiber membranes, such as Figure 2 c1. Figure 2 d1 and Figure 2 As shown in e1, they are the surface electron micrographs of MOFs / porous fiber membranes of Examples 1, 2, and 3, respectively. Figure 2 c2, Figure 2 d2 and Figure 2 e2 are cross-sectional electron micrographs of MOFs / porous fiber membranes of Examples 1, 2, and 3, respectively.

[0065] Compared with the fiber membrane (blank control) and the porous fiber membrane (Comparative Example 1), there are a large number of uniform MOFs particles on the surface and cross-section of the MOFs / porous fiber membrane, indicating that Examples 1 to 3 have successfully prepared MOFs / porous fiber membranes.

[0066] 2. Antibacterial test

[0067] The antibacterial activity of five samples of MOFs / porous fiber membrane, porous fiber membrane (Comparative Example 1) and fiber membrane (blank control) prepared in Examples 1 to 3 was evaluated by the inhibition zone method. Escherichia coli, Staphylococcus aureus and Aspergillus niger were used as model bacteria. First, 70 μL of Escherichia coli, Staphylococcus aureus and Aspergillus niger suspensions were applied to the surface of the culture medium. Afterwards, the above five samples placed under ultraviolet light disinfection were cut into discs of d = 7 mm and attached to the culture medium containing the bacterial solution. Finally, the samples were placed in an incubator at 37°C for 1 day and photographed.

[0068] The inhibition zone effects of fiber membrane (blank control), porous fiber membrane (comparative example 1), MOFs / porous fiber membrane (examples 1 to 3) on Escherichia coli, Staphylococcus aureus and Aspergillus niger are as follows Figure 3As shown, the inhibition zone of MOFs / porous fiber membrane can be retained for 3 days. The blank control, comparative example 1 and examples 1 to 3 are Figure 3 The test results of the antibacterial properties of fiber membrane (blank control), porous fiber membrane (Comparative Example 1), MOFs / porous fiber membrane (Examples 1-3) against Escherichia coli, Staphylococcus aureus and Aspergillus niger are shown in Table 1.

[0069] Combination Figure 3 From the results in Table 1, it can be seen that the fiber membrane (blank control) and the porous fiber membrane (comparative example 1) have no antibacterial properties against Escherichia coli, Staphylococcus aureus and Aspergillus niger. When MOFs are successfully grown on the modified fiber membrane, the prepared MOFs / porous fiber membranes (Examples 1 to 3) have good antibacterial properties against Escherichia coli, Staphylococcus aureus and Aspergillus niger.

[0070] Table 1. Diameters of inhibition zones of MOFs / porous fiber membrane materials against Escherichia coli, Staphylococcus aureus and Aspergillus niger

[0071] Test samples Escherichia coli Staphylococcus aureus Aspergillus niger Blank control 0 0 0 Comparative Example 1 0 0 0 HKUST-1 / CMWP 2.17±0.31 1.93±0.12 6.05±0.73 ZIF-8 / CMWP 0 2.92±0.17 5.35±0.46 ZIF-67 / CMWP 6.05±0.74 1.19±0.14 3.72±0.38

[0072] 3. Photocatalytic test

[0073] The MOFs / porous cellulose membrane prepared in Example 3 was subjected to photocatalytic degradation of cephalexin under irradiation of a 500 W xenon lamp (λ>420 nm), and the test method was as follows.

[0074] Take 0.7g of the MOFs / porous cellulose membrane prepared in Example 3 or the control fiber membrane and place it in a photoreactor, and add 100 mL (5 mg / L) of cephalexin aqueous solution to the reactor. The photoreactor was placed in complete darkness and magnetically stirred for 30 min to reach adsorption-desorption equilibrium. Then, the photoreactor was exposed to a xenon lamp for photocatalytic degradation reaction, and circulating water was used to keep the system temperature consistent (30°C). 1 mL of the mixed solution was collected every 1 h, filtered with a 0.22 μm filter membrane, and the residual concentration of cephalexin was analyzed by high performance liquid chromatography.

[0075] The degradation rates of antibiotic photodegradation by MOFs / porous fiber membranes in comparative example 2 and example 3 are shown in Table 2. The results show that comparative example 2 has no degradation effect on antibiotics (5 mg / L). The MOFs / porous cellulose membrane prepared in example 3 photodegrades antibiotics (5 mg / L) and can achieve complete degradation in 3 hours.

[0076] Table 2. Test of the photodegradation performance of fiber membrane and MOFs / porous fiber membrane materials on antibiotics (degradation rate %)

[0077] Sample Comparative Example 2 Example 3 0h 0 0 1h 0 76.95±1 2h 0 87.24±0.73 3h 0 99.98±0.02 4h 0 100

[0078] The electron microscope images of Comparative Example 2 and MOFs / porous fiber membrane (Example 3) are as follows: Figure 4 and Figure 5 As shown in the figure, it can be seen that when there is no sodium chloroacetate, there are only hydroxyl groups on the fiber molecular chain, and the binding force between hydroxyl groups and MOFs is relatively weak, that is, the binding is not firm, and the MOFs grow very little on the fiber surface and are unevenly dispersed. However, there are a large number of evenly distributed carboxymethyl groups on the fiber surface after carboxymethylation, which makes a large number of MOFs grow on the fiber surface and bind firmly. This leads to a significant difference in their photodegradation performance (Table 2).

[0079] 4. Regeneration cycle stability of MOFs / porous fiber membranes

[0080] In order to evaluate the recyclability of the MOFs / porous fiber membrane of Example 3, we regenerated the photodegraded MOFs / porous fiber membrane of Example 3.

[0081] The MOFs / porous fiber membrane can be regenerated by processing the steps (2) and (3) of the preparation method again. This embodiment refers to the steps (2) and (3) of Example 3 for regeneration. When the MOFs / porous fiber membrane prepared in Example 3 is used for antibiotic degradation after the fifth regeneration, the antibiotic can still be completely degraded within 4 hours. This result shows that the MOFs / porous fiber membrane prepared by the present invention has good photocatalytic degradation stability and regeneration stability for antibiotics.

Claims

1. A functionalized MOFs / porous fiber membrane, characterized in that: The MOFs / porous fiber membrane is prepared by in-situ synthesis of MOFs on a porous fiber membrane; the content of MOFs in the MOFs / porous fiber membrane is 16 wt% to 25 wt%.

2. The functionalized MOFs / porous fiber membrane according to claim 1, characterized in that: The MOFs is at least one of UIO-66, MIL-101, HKUST-1, ZIF-8, ZIF-67, and UIO-66-NH2.

3. The functionalized MOFs / porous fiber membrane according to claim 1, characterized in that: The fiber membrane is at least one of filter paper, cotton, wool, soybean protein fiber and polyvinyl chloride fiber.

4. A method for preparing the functionalized MOFs / porous fiber membrane according to any one of claims 1 to 3, characterized in that: The steps include: S1: soaking the fiber membrane in an organic solvent, adding alkali solution for reaction, then adding sodium chloroacetate to the reaction system for reaction, and reacting at a certain temperature for 3 to 5 hours to obtain a porous fiber membrane; S2: Add the porous fiber membrane to a mixed solution of an organic ligand solution and a metal salt solution, and then continue to add the organic ligand solution and the metal salt solution to immerse the porous fiber membrane, and react at 30 to 50° C. for 5 to 20 hours to obtain a MOFs / porous fiber membrane.

5. The preparation method according to claim 4, characterized in that: The concentration of sodium chloroacetate in the reaction system is 30-60 g / L.

6. The preparation method according to claim 4, characterized in that: The reaction temperature in step S1 is 35-50°C.

7. The preparation method according to claim 4, characterized in that: The volume ratio of the organic ligand solution to the metal salt solution in the mixed solution in step S2 is 1:1; the volume ratio of the organic ligand solution continued to be added in step S2 to the metal salt solution is 1:1; the concentration of the organic ligand in the organic ligand solution is 2-5 g / L; the concentration of the metal salt in the metal salt solution is 3-13 g / L.

8. A method for regenerating a functionalized MOFs / porous fiber membrane, characterized in that: The steps include: The MOFs / porous fiber membrane can be regenerated by treating the MOFs / porous fiber membrane again according to step S2 of claim 4.

9. The use of the functionalized MOFs / porous fiber membrane in antibacterial applications according to any one of claims 1 to 3, characterized in that: The MOFs / porous fiber membrane has an inhibitory effect on Escherichia coli, Staphylococcus aureus and Aspergillus niger.

10. The use of the functionalized MOFs / porous fiber membrane according to any one of claims 1 to 3 in photocatalytic degradation of antibiotics, characterized in that: The antibiotics include cephalexin.

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