CN111203199B - Porous beta-cyclodextrin cross-linked polymer nanofiber, preparation method thereof and application of porous beta-cyclodextrin cross-linked polymer nanofiber in removing bisphenol organic pollutants in water body - Google Patents
Porous beta-cyclodextrin cross-linked polymer nanofiber, preparation method thereof and application of porous beta-cyclodextrin cross-linked polymer nanofiber in removing bisphenol organic pollutants in water body Download PDFInfo
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Abstract
The invention relates to a porous beta-cyclodextrin cross-linked polymer nanofiber, a preparation method thereof and application thereof in removing bisphenol organic pollutants in water, relating to the technical field of nano materials. The technical problems of low adsorption binding capacity and low removal efficiency of low-concentration pollutants in the process of efficiently adsorbing and removing bisphenol organic pollutants in water by using the conventional beta-cyclodextrin polymer adsorbent are solved. The porous beta-cyclodextrin cross-linked polymer nanofiber provided by the invention is prepared by taking a beta-cyclodextrin-copper metal organic framework nano material as a template, the obtained polymer has a large specific surface area, the beta-cyclodextrin molecules in the polymer retain a dimer ordered tubular arrangement mode in the metal organic framework material, and the dimer structure can form a stable host-guest inclusion compound with bisphenol pollutant molecules through a synergistic effect, so that the cross-linked polymer has strong adsorption affinity and good adsorption performance on bisphenol pollutants in a water body.
Description
Technical Field
The invention relates to the technical field of nano materials, in particular to porous beta-cyclodextrin cross-linked polymer nano fibers, a preparation method thereof and application thereof in removing bisphenol organic pollutants in water.
Background
Bisphenol compounds including bisphenol A (BPA), bisphenol B (BPB), bisphenol F (BPF), bisphenol S (BPS) are one of the common organic pollutants in water. These compounds are widely used in industrial production of plastics, synthetic resins, and the like, and they are also environmental endocrine disruptors which are attracting much attention. When these bisphenols are ingested by the human body or aquatic organisms, they can interfere with their endocrine system by mimicking the organism's own hormones, thereby posing a significant threat to the health of the organism. There is no specific effective method for removing bisphenol pollutants in water body in the current water treatment system. The adsorption effect of activated carbon as a common method for removing organic pollutants in water bodies is unsatisfactory for bisphenol compounds, which is mainly because the interaction between bisphenol compounds and activated carbon is hindered by the non-planar molecular structure of the bisphenol compounds. In addition, the low adsorption rate of the activated carbon and the high production and regeneration cost are also important factors for limiting the application of the activated carbon as an adsorption material. These limitations are also present in other common adsorbent materials such as clay materials and zeolite adsorbent materials. In recent decades, with the vigorous development of nanotechnology, some emerging nano-adsorption materials such as graphene, carbon nanotubes, molecularly imprinted nanomaterials, metal-organic framework materials and the like are also applied to adsorption of bisphenol pollutants in water bodies, and compared with the traditional adsorbents, the materials have higher porosity, specific surface area and the like, so that the adsorption rate, adsorption selectivity, adsorption efficiency and the like are greatly improved, but the materials still face the problems of complex preparation process, low material stability and the like. More importantly, the separation of the nano-adsorption material is difficult, the column pressure is easily overhigh after the nano-adsorption material is filled into the adsorption column, and great inconvenience is brought to the actual water treatment process. Furthermore, for most current adsorbent materials, it is still not efficient in removing low levels of bisphenol contaminants in water, mainly because the adsorption properties of the adsorbent material are directly related to its porosity, specific surface area and surface properties (i.e., the interaction between the material and the adsorbed contaminant molecules). Generally speaking, the higher the porosity and the larger the specific surface area of the material, the more favorable the adsorption of the pollutant. However, for the adsorption of bisphenol pollutants at low concentration, the affinity between the adsorption material and the pollutant molecules, i.e. the adsorption binding constant, is the most important factor for determining the adsorption effect of the material. Therefore, it is of great importance to develop new highly efficient adsorbent materials to cope with the growing water contamination problem of bisphenol compounds.
The beta-cyclodextrin is a hollow cylindrical three-dimensional conical molecule, and the inner hydrophobic structure and the outer hydrophilic structure of the beta-cyclodextrin enable the beta-cyclodextrin to form a host-guest inclusion compound with organic matters with matched sizes through interaction such as hydrophobic-hydrophobic interaction, intermolecular interaction and the like. Based on this, the research on the application of beta-cyclodextrin and its derivatives in removing organic pollutants in water has received great attention in recent years. However, the beta-cyclodextrin is easily soluble in water and cannot be directly applied to sewage treatment, and the beta-cyclodextrin serving as a sewage treatment adsorption material is made possible by converting cyclodextrin molecules into a cross-linked polymer which is insoluble in water in a chemical cross-linking mode. Beta-cyclodextrin cross-linked polymer has the characteristics of simple preparation method, high adsorption rate and easy cyclic recycling, and in recent years, a great deal of research work is devoted to improving the adsorption performance of the beta-cyclodextrin polymer material on bisphenol pollutants from the aspects of regulating and controlling the components, structural characteristics and the like of the beta-cyclodextrin polymer material, but little research work is devoted to optimizing the adsorption performance of the beta-cyclodextrin polymer material from regulating and controlling the microstructure of the beta-cyclodextrin polymer, such as the arrangement mode of beta-cyclodextrin molecules in the polymer.
As is well known, the binding constant of the inclusion complex formed by the beta-cyclodextrin molecule and the guest molecule is positively correlated with the surface area of the molecule embedded into the hydrophobic cavity of the cyclodextrin, and the larger the area of the guest molecule entering the cavity is, the stronger the interaction between the guest molecule and the cyclodextrin molecule is, and the larger the binding constant is. Because the bisphenol compound molecule contains two phenol structures, the molecule is large and the structure is distorted, and only one phenol structure can enter the cavity of the beta-cyclodextrin molecule through the interaction of a host and a guest according to the principle of matching the size of the molecule. Studies have shown that cyclodextrin dimers bind much more strongly to size-matched organic molecules than individual cyclodextrin molecules due to the presence of a "synergistic effect". Therefore, we assume that if β -cyclodextrin dimers are subjected to ordered arrangement directed polymerization to form β -cyclodextrin polymers, the resulting materials should have strong binding capacity and high adsorption efficiency for bisphenols. However, the traditional polymerization reaction which occurs through the random combination of the cross-linking molecules and the beta-cyclodextrin molecules is difficult to form a polymer structure with orderly arranged cyclodextrin molecules. Although the literature reports that the beta-cyclodextrin dimer rotaxane is used as a template to synthesize the beta-cyclodextrin nanometer molecular pipeline polymer, the method has the disadvantages of complicated synthesis steps and low yield, and the obtained polymer is soluble in water, so that the method is not favorable for large-scale application of the polymer as an adsorbent material in the field of sewage treatment.
Disclosure of Invention
The invention aims to solve the technical problems of low adsorption binding capacity and low removal efficiency of low-concentration pollutants in the process of efficiently adsorbing and removing bisphenol organic pollutants in water by using the conventional beta-cyclodextrin polymer adsorbent, and provides porous beta-cyclodextrin cross-linked polymer nano fibers with excellent adsorption performance, a preparation method thereof and application thereof in removing bisphenol organic pollutants in water.
In order to solve the technical problems, the technical scheme of the invention is as follows:
the invention provides a porous beta-cyclodextrin cross-linked polymer nanofiber, which is prepared by taking beta-cyclodextrin-copper (Cu) metal organic framework nano materials (beta-CD-Cu MOF NFs) as templates and 2, 4-toluene diisocyanate (2,4-TDI) as a cross-linking agent, wherein beta-cyclodextrin (beta-CD) molecules are orderly arranged in a dimer structure to form the porous beta-cyclodextrin cross-linked polymer nanofiber (beta-CD NFs).
The invention also provides a preparation method of the porous beta-cyclodextrin cross-linked polymer nanofiber, which comprises the following steps:
(1) using water as solvent, beta-CD, sodium hydroxide (NaOH), and copper chloride dihydrate (CuCl)2·2H2O) fully mixing and dissolving, filtering to remove insoluble substances, pouring absolute ethyl alcohol into filtrate, washing obtained precipitate with the ethyl alcohol, and performing vacuum drying to obtain blue solid, namely beta-cyclodextrin-Cu metal organic framework template materials (beta-CD-Cu MOF NFs);
(2) stirring and reacting beta-CD-Cu MOF NFs and 2,4-TDI under an argon atmosphere by taking anhydrous N, N-Dimethylformamide (DMF) as a solvent and dibutyltin dilaurate as a catalyst; and after the reaction is finished, centrifuging a product obtained by the reaction, washing the product with DMF (dimethyl formamide), and then washing the product with dilute hydrochloric acid and water respectively to obtain the milky white porous beta-cyclodextrin cross-linked polymer nanofibers (beta-CD NFs).
In the above technical solution, in the step (1): beta-CD, NaOH, CuCl2·2H2Feeding O in a molar ratio of 0.005:1: 0.01.
In the above technical solution, in the step (1): dissolving beta-CD and NaOH in water, and adding CuCl2·2H2And mixing the O aqueous solution uniformly.
In the above technical solution, in the step (2): feeding beta-CD-Cu MOF NFs and 2,4-TDI according to the mass ratio of 5: 3.
In the above technical solution, in the step (2): firstly dispersing beta-CD-Cu MOF NFs in DMF, then adding dibutyltin dilaurate, uniformly stirring, and finally adding 2, 4-TDI.
In the above technical solution, in the step (2): the reaction temperature was 75 ℃ and the reaction time was 24 h.
The invention also provides application of the porous beta-cyclodextrin cross-linked polymer nanofiber in removing bisphenol organic pollutants in a water body.
In the technical scheme, the porous beta-cyclodextrin cross-linked polymer nanofiber is required to be modified on cotton fabric fibers to obtain a composite adsorption material, and then the composite adsorption material is used for removing bisphenol organic pollutants in a water body.
In the technical scheme, the composite adsorption material is prepared by the following method:
(1) uniformly dispersing beta-CD-Cu MOF NFs in absolute ethyl alcohol, immersing cotton fabric fibers in the absolute ethyl alcohol, taking out the cotton fabric fibers, and drying the cotton fabric fibers at room temperature to obtain the cotton fabric modified by the beta-CD-Cu MOF NFs;
(2) taking anhydrous DMF as a solvent, respectively adding dibutyltin dilaurate and 2,4-TDI, stirring and mixing uniformly, then adding the cotton fabric modified by beta-CD-Cu MOF NFs, reacting for 48 hours under the argon atmosphere and mild stirring at 75 ℃, finally soaking and washing the obtained cotton fabric twice in DMF, diluted hydrochloric acid and water respectively, and obtaining the cotton fabric modified by the beta-CD NFs.
The invention has the beneficial effects that:
the porous beta-cyclodextrin cross-linked polymer nanofiber provided by the invention is prepared by taking beta-cyclodextrin-copper (Cu) metal organic framework nano materials (beta-CD-Cu MOF NFs) as templates, the obtained polymer has a large specific surface area, dimer ordered tubular arrangement modes of the beta-cyclodextrin molecules in the metal organic framework materials are reserved in the interior of the polymer, and the dimer structures and bisphenol pollutant molecules can form stable host-guest inclusion compounds through synergistic effects, so that the cross-linked polymer has strong adsorption affinity and good adsorption performance on bisphenol pollutants in a water body.
The preparation method of the porous beta-cyclodextrin cross-linked polymer nanofiber adopts the beta-cyclodextrin metal organic framework nano material as a template, the template material can be synthesized by a one-step precipitation method, the yield is high, and the synthesis scale can be enlarged by simply increasing the amount of reactants. The obtained template material is firstly subjected to a cross-linking reaction between ligand molecule 2, 4-Toluene Diisocyanate (TDI) and hydroxyl groups which are not coordinated with metal on cyclodextrin molecules in a metal organic framework, and then metal ions are removed by washing to destroy metal-hydroxyl coordination bonds, so that the porous beta-cyclodextrin polymer nanofibers (beta-CD NFs) with beta-cyclodextrin molecules orderly arranged in a dimer form are synthesized. The nanofiber keeps the shape and structure of a template material, has high beta-cyclodextrin content, shows strong adsorption binding capacity and high adsorption efficiency on typical bisphenol compounds (BPA, BPB, BPF and BPS), and has an equilibrium adsorption coefficient (Kd) of 10 to BPA5Lmol-1Higher than most of the reported adsorbing materials. The invention discusses the adsorption process and the adsorption mechanism of the material through an experimental and theoretical calculation method, and proves that the high-efficiency adsorption performance of the porous nanofiber mainly comes from the ordered arrangement of beta-cyclodextrin dimer in the structure, the structure not only enhances the binding capacity (synergistic effect) of the beta-cyclodextrin dimer on bisphenol molecules, but also improves the utilization rate of the beta-cyclodextrin dimer (the porosity of the material enables the cyclodextrin dimer in the structure to be contacted by pollutant molecules).
The porous beta-cyclodextrin cross-linked polymer nanofiber can be used for removing bisphenol organic pollutants in a water body, the nanofiber can be modified on cotton fabric through an in-situ polymerization method, the problem that a nano adsorption material is difficult to separate in the actual water treatment process can be effectively solved, the obtained cotton fabric is used for replacing an activated carbon material and used on a commercial water purification filter, the removal efficiency of the obtained water purification equipment on trace bisphenol A in drinking water is higher than that of the activated carbon filter, and the content of bisphenol A in the treated drinking water can reach a limit standard lower than that of the drinking water. The simple water purifier prepared from the cotton fabric has obviously better adsorption effect on trace bisphenol pollutants in drinking water than a commercial activated carbon water purifier. The invention provides a new idea for improving the removal efficiency of the cyclodextrin adsorption material on the organic pollutants in the water body.
Drawings
The present invention will be described in further detail with reference to the accompanying drawings and specific embodiments.
FIG. 1 is a crystal structure diagram of β -CD-Cu MOF NFs, wherein A) is a single crystal analysis structure diagram of β -CD-Cu MOF NFs, and B) is a structure diagram of dimers formed by coordination of β -CD with metal ions in β -CD-Cu MOF NFs.
FIG. 2 is N of beta-CD NFs2Adsorption isotherms and pore size distribution plots.
FIG. 3 is an electron microscopy characterization of β -CD NFs and cotton fabrics modified therefrom, wherein β -CD-Cu MOF NFsa), β -CD-Cu MOF NFs b) after 2.4-TDI crosslinking, and β -CD NFs c) (the top left inside is a transmission electron microscopy characterization corresponding thereto, with a scale of 500 nm); scanning electron micrographs of commercial cotton fabric fibers d), beta-CD-Cu MOF NFs modified cotton fabric fibers e), and beta-CD NFs modified cotton fabric fibers f); commercial cotton fabric g), β -CD-Cu MOF NFs modified cotton fabric h), and β -CDNFs modified cotton fabric i).
FIG. 4 is a graph of adsorption efficiency of β -CD NFs against bisphenol contaminants, wherein a) β -CD NFs against bisphenol A (BPA), bisphenol B (BPB), bisphenol F (BPF), and bisphenol S (BPS) is plotted against time; b) adsorption efficiencies of β -CD NFs for BPA, BPB, BPF and BPS are reached at adsorption equilibrium.
FIG. 5 is a Langmuir adsorption isotherm for β -CD NFs versus BPA a), BPB b), BPF c) and BPS d).
In FIG. 6, a) a real object diagram of the water purifier is shown, wherein I) a self-made filter element and II) a commercial activated carbon filter element are arranged; b) the self-made water purifier and the activated carbon water purifier have the efficiency of removing four bisphenol pollutants simultaneously existing in drinking water.
Detailed Description
Example 1: preparation and Synthesis of beta-CD NFs
(1) 24g NaOH, 3.405g beta-CD was dissolved in 130mL water, and 1.023g CuCl was added2·2H2Dissolving O in 20mL of water, mixing and stirring the two solutions uniformly, filtering to remove precipitates, adding 200mL of absolute ethyl alcohol into the obtained filtrate, separating out light blue precipitates, slightly shaking the solution, after the precipitates are separated out fully, centrifuging, washing the precipitates for 2-3 times by using the absolute ethyl alcohol, and drying in vacuum to obtain the beta-CD-Cu MOFNFs.
Referring to fig. 1, in the structure of the β -CD-Cu MOF NFs, two β -CD molecules coordinate with four copper ions and five sodium ions through their secondary hydroxyl groups (13) to form cyclodextrin dimers (fig. 1B), which are connected by hydrogen bonding between primary hydroxyl groups of β -CD to form a two-dimensional nanotube-shaped structure, respectively (fig. 1B). The nanotubes are bonded by metal bridge oxygen
(as shown in FIG. 1A: Na1-Na13-Na12, Na3-Na11-Na6, Na5-Na8) are connected to form a three-dimensional structure.
(2) Under the argon atmosphere, suspending and dispersing 2g of prepared beta-CD-Cu MOF NFs in 30mL of anhydrous DMF, adding 1 drop (about 50 mu L) of dibutyltin dilaurate, stirring uniformly, adding 1.2g of 2,4-TDI (dissolved in 10mL of anhydrous DMF), heating to 75 ℃, and stirring for reacting for 24 h; the reaction was then collected by centrifugation, washed twice with DMF to remove reaction residues, then washed twice with dilute hydrochloric acid (0.1M), water, and dried under vacuum to give β -CD NFs. Yield: 15 percent.
The results of the porosity characterization (nitrogen adsorption and desorption experiment) of the obtained beta-CD NFs are shown in FIG. 2, and the specific surface area of the beta-CD NFs is 150m calculated by a BET theoretical model2 g-1The pore size distribution peaks of the beta-CD NFs calculated by the BJH model are mostly distributed within 20nm, which indicates that the mesoporous structure is formed on the material.
Example 2: preparation synthesis of cotton fabric modified by beta-CD NFs
(1) 0.1g of beta-CD-Cu MOF NFs prepared in the step (1) of the reference example 1 is suspended and dispersed in 30mL of absolute ethyl alcohol, a cotton fabric is added, the cotton fabric is taken out after being soaked, and the cotton fabric is dried at room temperature, so that the cotton fabric modified by the beta-CD-Cu MOF NFs can be obtained.
(2) Under argon atmosphere, 2.4g of 2,4-TDI, 2 drops (about 100. mu.L) of dibutyltin dilaurate were dissolved in 80mL of anhydrous DMF, about thirty sheets of β -CD-CuMOF NFs-modified cotton fabric having a diameter of 7cm and a thickness of about 1mm were added, and the reaction was stirred at 75 ℃ for 48 hours. And then taking the cotton fabric out, and soaking and washing the cotton fabric in DMF (dimethyl formamide), dilute hydrochloric acid (0.1M) and water twice respectively to obtain the cotton fabric modified by the beta-CD NFs.
An electron microscope characterization diagram of the obtained beta-CD NFs modified cotton fabric is shown in figure 3, and it can be known from figures 3a to 3c that beta-CD-Cu MOF NFs, beta-CD-Cu MOF NFs after cross-linking reaction and the obtained beta-CD NFs are all in a nanofiber-like structure, the length is about 5-10 muL, and the width is about 200 nm; FIGS. 3d-3f and 3g-3i are respectively an electron microscope representation and a physical image of the cotton fabric before and after the material modification, and the results show that the beta-CD NFs are successfully modified on the cotton fabric.
Example 3: adsorption experiment of bisphenol contaminants
(1) Adding 0.10g of prepared beta-CD NFs into an erlenmeyer flask containing 50mL of water, uniformly dispersing by ultrasonic wave, respectively adding 50mL of 0.2mM bisphenol A (bisphenol B, bisphenol F or bisphenol S) solution (the final concentration of the beta-CD NFs in the solution is 1mg/mL), placing the erlenmeyer flask in a water bath at 25 ℃, and magnetically stirring (500 r/min)-1) And (5) 24 h. 2mL of the above solutions were taken out at different time points, respectively, filtered, and absorbance was measured at the maximum absorption wavelength of the bisphenol compound with an ultraviolet-visible spectrophotometer to determine the concentration of the contaminant in the solution after adsorption, to calculate the adsorption amount and the adsorption efficiency.
FIG. 4 is a graph of the adsorption efficiency of β -CD NFs on bisphenol A (BPA), bisphenol B (BPB), bisphenol F (BPF) and bisphenol S (BPS) over time. b) Adsorption efficiencies of β -CD NFs for BPA, BPB, BPF and BPS are reached at adsorption equilibrium.
FIG. 5 is a Langmuir adsorption isotherm for β -CD NFs versus BPA a), BPB b), BPF c) and BPS d).
(2) The adsorption results show that: after the beta-CD NFs are adsorbed, the concentration of four bisphenol pollutants is greatly reduced, and particularly for bisphenol A and bisphenol B, the adsorption rate of the material to the beta-CD NFs can be higher than 99% when the initial concentration of the pollutants is 0.1mM under the conditions that the dosage of the beta-CD NFs is 1mg/mL and the temperature is 25 ℃; under the same conditions, the adsorption rates of beta-CD NFs for bisphenol F and bisphenol S also reached 94% and 92%, respectively (FIG. 4). The adsorption binding constant (K) of the beta-CD NFs to the bisphenol A can be as high as 10 at 25 ℃ by using the Langmuir isothermal adsorption equation at the dosage of the beta-CD NFs of 1mg/mL5L/mol, higher than that of the beta-CD polymer water purification adsorption material (figure 5).
Example 4: adsorption experiment of simple water purifier with beta-CD NFs modified cotton fabric as adsorption material on trace bisphenol pollutants in drinking water
Taking out the adsorption material in the commercial activated carbon water purifier, then putting cotton fabrics modified by beta-CD NFs into the adsorption material, and putting quartz sand as a support material to be alternately stacked with the cotton fabrics to prepare the simple water purifier. 1L of drinking water containing bisphenol A (concentration of 50ppb) and 500mL of drinking water containing BPA, BPB, BPF and BPS (concentration of 50ppb respectively) are added into a water purifier, the filtered drinking water is taken out, and the content of bisphenol pollutants in the drinking water is detected by high performance liquid chromatography.
The adsorption results show that: the simple water purifier prepared by the invention has good adsorption capacity on trace bisphenol pollutants in drinking water, and the content (6.191ppb) of bisphenol A in the filtered drinking water can reach a limit standard (10ppb) lower than that of bisphenol A in national drinking water. In addition, the water purifier can simultaneously remove four typical bisphenol pollutants (BPA, BPB, BPF and BPS) in drinking water, and the removal efficiency can reach more than 70 percent respectively. Under the same conditions, the removal efficiency of the commercial activated carbon water purifier to four bisphenol compounds is not more than 50% (fig. 6).
It should be understood that the above examples are only for clarity of illustration and are not intended to limit the embodiments. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. And are neither required nor exhaustive of all embodiments. And obvious variations or modifications therefrom are within the scope of the invention.
Claims (10)
1. A porous beta-cyclodextrin cross-linked polymer nanofiber is characterized in that a beta-cyclodextrin-copper metal organic framework nano material is used as a template, 2, 4-toluene diisocyanate is used as a cross-linking agent, and the porous beta-cyclodextrin cross-linked polymer nanofiber with beta-cyclodextrin molecules orderly arranged in a dimer structure is prepared.
2. A method for preparing the porous beta-cyclodextrin cross-linked polymer nanofiber as claimed in claim 1, comprising the steps of:
(1) taking water as a solvent, fully mixing and dissolving beta-cyclodextrin, sodium hydroxide and copper chloride dihydrate, filtering to remove insoluble substances, pouring absolute ethyl alcohol into filtrate, washing obtained precipitate with ethanol, and drying in vacuum to obtain a blue solid, namely the beta-cyclodextrin-copper metal organic framework template material;
(2) stirring and reacting a beta-cyclodextrin-copper metal organic framework template material and 2, 4-toluene diisocyanate by taking anhydrous N, N-dimethylformamide as a solvent and dibutyltin dilaurate as a catalyst in an argon atmosphere; and after the reaction is finished, centrifuging a product obtained by the reaction, washing the product by using N, N-dimethylformamide, and then washing the product by using dilute hydrochloric acid and water respectively to obtain the milky porous beta-cyclodextrin crosslinked polymer nanofiber.
3. The method for preparing porous beta-cyclodextrin cross-linked polymer nanofiber according to claim 2, wherein in the step (1): beta-cyclodextrin, sodium hydroxide and copper chloride dihydrate are fed in a molar ratio of 0.005:1: 0.01.
4. The method for preparing porous beta-cyclodextrin cross-linked polymer nanofiber according to claim 2, wherein in the step (1): dissolving beta-cyclodextrin and sodium hydroxide in water, adding copper chloride dihydrate water solution, and mixing.
5. The method for preparing porous beta-cyclodextrin cross-linked polymer nanofiber according to claim 2, wherein in the step (2): feeding the beta-cyclodextrin-copper metal organic framework template material and 2, 4-toluene diisocyanate according to the mass ratio of 5: 3.
6. The method for preparing porous beta-cyclodextrin cross-linked polymer nanofiber according to claim 2, wherein in the step (2): firstly, dispersing a beta-cyclodextrin-copper metal organic framework template material in N, N-dimethylformamide, then adding dibutyltin dilaurate, uniformly stirring, and finally adding 2, 4-toluene diisocyanate.
7. The method for preparing porous beta-cyclodextrin cross-linked polymer nanofiber according to claim 2, wherein in the step (2): the reaction temperature was 75 ℃ and the reaction time was 24 h.
8. The application of the porous beta-cyclodextrin cross-linked polymer nanofiber as claimed in claim 1 in removing bisphenol organic pollutants in a water body.
9. The use of claim 8, wherein the porous beta-cyclodextrin cross-linked polymer nanofibers are modified onto cotton fabric fibers to obtain a composite adsorbent material, and then the composite adsorbent material is used for removing bisphenol organic pollutants in a water body.
10. The use according to claim 9, wherein the composite adsorbent material is prepared by a method comprising:
(1) uniformly dispersing the beta-cyclodextrin-copper metal organic framework template material in absolute ethyl alcohol, soaking cotton fabric fibers in the absolute ethyl alcohol, taking out the cotton fabric fibers, and drying the cotton fabric fibers at room temperature to obtain cotton fabric modified by the beta-cyclodextrin-copper metal organic framework template material;
(2) the preparation method comprises the steps of taking anhydrous N, N-dimethylformamide as a solvent, respectively adding dibutyltin dilaurate and 2, 4-toluene diisocyanate, stirring and mixing uniformly, then adding a cotton fabric modified by a beta-cyclodextrin-copper metal organic framework template material, reacting for 48 hours under the argon atmosphere and mild stirring at 75 ℃, finally soaking and washing the obtained cotton fabric in N, N-dimethylformamide, diluted hydrochloric acid and water for two times, and obtaining the cotton fabric modified by the porous beta-cyclodextrin cross-linked polymer nanofiber.
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