CN111203199A - Porous β -cyclodextrin cross-linked polymer nanofiber, preparation method thereof and application thereof in removing bisphenol organic pollutants in water body - Google Patents
Porous β -cyclodextrin cross-linked polymer nanofiber, preparation method thereof and application thereof in removing bisphenol organic pollutants in water body Download PDFInfo
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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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Abstract
The invention relates to a porous β -cyclodextrin cross-linked polymer nanofiber, a preparation method thereof and application thereof in removing bisphenol organic pollutants in a water body, relates to the technical field of nanomaterials, and solves the technical problems that an existing β -cyclodextrin polymer adsorbent is low in adsorption binding capacity and low in removal efficiency of low-concentration pollutants in the process of efficiently adsorbing and removing the bisphenol organic pollutants in the water body.
Description
Technical Field
The invention relates to the technical field of nano materials, in particular to porous β -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. Activated carbon adsorption, which is a common method for removing organic pollutants in water, has unsatisfactory adsorption effect on bisphenol compounds, 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 costs are also important factors 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 adsorbent, 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 performance of the adsorbent material is 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.
β -cyclodextrin is a hollow cylindrical three-dimensional cone-shaped molecule, the inner hydrophobic structure and the outer hydrophilic structure of which enable the molecule to form a host-guest inclusion compound through the interaction of hydrophobic-hydrophobic and intermolecular force and the like with organic matters matched with the size, based on the above, the research of β -cyclodextrin and derivatives thereof for removing organic pollutants in water bodies has received great attention in recent years, however, β -cyclodextrin is easily soluble in water and cannot be directly applied to sewage treatment, the cyclodextrin molecules are converted into cross-linked polymers which are difficult to dissolve in water through a chemical cross-linking mode, so that β -cyclodextrin can be used as a sewage treatment adsorbing material, β -cyclodextrin cross-linked polymer has the characteristics of simple preparation method, fast adsorption rate and easy recycling, and in recent years, a great deal of research work is devoted to regulating and controlling the components, structural characteristics and the like of β -cyclodextrin polymer materials to improve the adsorption performance of bisphenol pollutants, but the research work is devoted to regulating and controlling the microstructure of β -cyclodextrin polymers, for example, the arrangement mode of β -cyclodextrin molecules in the polymers is used for optimizing the adsorption performance of bisphenol pollutants.
It is known that β -the binding constant of the inclusion complex formed by the cyclodextrin molecule and the guest molecule is positively correlated with the surface area of the molecule embedded into the hydrophobic cavity of cyclodextrin, the larger the surface area of the guest molecule entering into the cavity, the stronger the interaction between the guest molecule and the cyclodextrin molecule, the larger the binding constant, because the bisphenol compound molecule contains two phenol structures, the larger the molecule is and the structure is distorted, according to the principle of matching the size of the molecule, only one phenol structure can enter into the β -cyclodextrin molecule cavity through the host-guest interaction.
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 β -cyclodextrin polymer adsorbent, and provides porous β -cyclodextrin cross-linked polymer nano-fibers with excellent adsorption performance, a preparation method thereof and application of the nano-fibers 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 β -cyclodextrin cross-linked polymer nanofiber, which is a porous β -cyclodextrin cross-linked polymer nanofiber (β -CD NFs) with β -cyclodextrin-copper (Cu) metal organic framework nano materials (β -CD-Cu MOF NFs) as templates and 2, 4-toluene diisocyanate (2,4-TDI) as a cross-linking agent, wherein β -cyclodextrin (β -CD) molecules are orderly arranged in a dimer structure.
The invention also provides a preparation method of the porous β -cyclodextrin cross-linked polymer nanofiber, which comprises the following steps:
(1) using water as solvent, β -CD, sodium hydroxide (NaOH), and cupric chloride dihydrate (CuCl)2·2H2O) fully mixing and dissolving, filtering to remove insoluble substances, pouring absolute ethyl alcohol into filtrate, washing obtained precipitate with ethanol, and vacuum drying to obtain a blue solid, namely β -cyclodextrin-Cu metal-organic framework template material (β -CD-Cu MOF NFs);
(2) stirring β -CD-Cu MOF NFs and 2,4-TDI under argon atmosphere by using anhydrous N, N-Dimethylformamide (DMF) as a solvent and dibutyltin dilaurate as a catalyst for reaction, centrifuging a product obtained by the reaction after the reaction is finished, washing the product with DMF, and then washing the product with dilute hydrochloric acid and water respectively to obtain the milky white porous β -cyclodextrin cross-linked polymer nanofibers (β -CD NFs).
In the technical scheme, in the step (1), β -CD, NaOH and CuCl are added2·2H2Feeding O in a molar ratio of 0.005:1: 0.01.
In the technical scheme, in the step (1), β -CD and NaOH are firstly dissolved in water, and then CuCl is added2·2H2And mixing the O aqueous solution uniformly.
In the technical scheme, β -CD-Cu MOF NFs and 2,4-TDI are fed in the step (2) according to the mass ratio of 5: 3.
In the technical scheme, in the step (2), β -CD-Cu MOF NFs are dispersed in DMF, dibutyltin dilaurate is added and stirred uniformly, and finally 2,4-TDI is added.
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 β -cyclodextrin cross-linked polymer nanofiber in removing bisphenol organic pollutants in a water body.
In the technical scheme, the porous β -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 β -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 at room temperature to obtain β -CD-Cu MOF NFs modified cotton fabric;
(2) taking anhydrous DMF as a solvent, respectively adding dibutyltin dilaurate and 2,4-TDI, stirring and mixing uniformly, then adding β -CD-Cu MOF NFs modified cotton fabric, carrying out mild stirring reaction for 48h at 75 ℃ under an argon atmosphere, and finally soaking and washing the obtained cotton fabric twice in DMF, dilute hydrochloric acid and water respectively to obtain β -CD NFs modified cotton fabric.
The invention has the beneficial effects that:
the porous β -cyclodextrin cross-linked polymer nanofiber provided by the invention is prepared by taking β -cyclodextrin-copper (Cu) metal organic framework nano materials (β -CD-Cu MOF NFs) as templates to prepare a porous β -cyclodextrin cross-linked polymer, the obtained polymer has a large specific surface area, dimer ordered tubular arrangement modes of the polymer in the metal organic framework materials are reserved in internal β -cyclodextrin molecules of the polymer, and a stable host-guest inclusion compound can be formed by the dimer structure and bisphenol pollutant molecules through a synergistic effect, so that the cross-linked polymer shows strong adsorption affinity and good adsorption performance to bisphenol pollutants in a water body.
The preparation method of porous β -cyclodextrin cross-linked polymer nanofiber adopts β -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 of 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 the metal-hydroxyl coordination bonds are destroyed by water washing to remove metal ions, so that the porous β -cyclodextrin polymer nanofiber (β -CD NFs) with β -cyclodextrin molecules orderly arranged in a dimer form is synthesizedThe nanofiber keeps the shape and the structure of a template material, has high β -cyclodextrin content, and shows strong adsorption binding capacity and high adsorption efficiency on typical bisphenol compounds (BPA, BPB, BPF and BPS), wherein the equilibrium adsorption coefficient (Kd) of the nanofiber on BPA can reach 105L mol-1The invention researches 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 is mainly derived from the ordered arrangement of β -cyclodextrin dimer in the structure, and the structure not only enhances the binding capacity (synergistic effect) of the nanofiber on bisphenol molecules, but also improves the utilization rate of β -cyclodextrin molecules (the porosity of the material enables the cyclodextrin molecules in the structure to be contacted by pollutant molecules).
The porous β -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 active carbon material and used on a commercial water purification filter, the removal efficiency of trace bisphenol A in drinking water of the obtained water purification equipment is higher than that of the active carbon filter, the content of bisphenol A in the treated drinking water can reach a level lower than the drinking water limit standard, the adsorption effect of a simple water purifier prepared from the cotton fabric is obviously better than that of the commercial active carbon water purifier, and a new thought is provided 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 analytical structure diagram of β -CD-Cu MOF NFs, and B) is a structure diagram of a dimer formed by coordination with metal ions of β -CD in β -CD-Cu MOF NFs.
FIG. 2 is N of β -CD NFs2Adsorption isotherm and pore sizeAnd (6) layout.
FIG. 3 is an electron microscope characterization image of β -CD NFs and cotton fabrics modified by the same, wherein β -CD-Cu MOF NFs a), β -CD-Cu MOF NFs b after 2.4-TDI crosslinking), and β -CD NFs c) (the top left inside is a corresponding transmission electron microscope characterization image with a scale of 500nm), commercial cotton fabric fiber d), β -CD-Cu MOF NFs modified cotton fabric fiber e), and β -CD NFs modified cotton fabric fiber f), commercial cotton fabric g), β -CD-Cu MOFNFs modified cotton fabric h), and β -CD NFs modified cotton fabric i).
FIG. 4 is a graph of adsorption efficiency of β -CD NFs for bisphenol contaminants, wherein a) β -CD NFs for bisphenol A (BPA), bisphenol B (BPB), bisphenol F (BPF) and bisphenol S (BPS) is plotted against time, and b) when adsorption equilibrium is reached, adsorption efficiency of β -CD NFs for BPA, BPB, BPF and BPS is shown.
FIG. 5 is a Langmuir adsorption isotherm of 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 of β -CD NFs Synthesis
(1) 24g NaOH, 3.405g β -CD were 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 sufficiently, centrifuging, washing the precipitates for 2-3 times by using the absolute ethyl alcohol, and drying in vacuum to obtain β -CD-Cu MOF NFs.
The crystal structure (single crystal resolution) of the β -CD-Cu MOF NFs is shown in FIG. 1, and in the β -CD-Cu MOF NFs structure, two β -CD molecules coordinate with four copper ions and five sodium ions through secondary hydroxyl groups (13) to form a cyclodextrin dimer form (FIG. 1B), and the dimers are connected through hydrogen bonding between primary hydroxyl groups of β -CD to form a two-dimensional nanotube-shaped structure
(as shown in FIG. 1A: Na1-Na13-Na12, Na3-Na11-Na6, Na5-Na8) are connected to form a three-dimensional structure.
(2) Under argon atmosphere, 2g of prepared β -CD-Cu MOF NFs are suspended and dispersed in 30mL of anhydrous DMF, 1 drop (about 50 mu L) of dibutyltin dilaurate is added, after uniform stirring, 1.2g of 2,4-TDI (dissolved in 10mL of anhydrous DMF) is added, the temperature is increased to 75 ℃, stirring is carried out for reaction for 24 hours, then reactants are centrifugally collected, the reactants are washed twice by DMF to remove reaction residues, then diluted hydrochloric acid (0.1M) and water are respectively used for washing twice, and vacuum drying is carried out to obtain β -CD NFs, wherein the yield is 15%.
Results of porosity characterization (nitrogen desorption experiment) of the obtained β -CD NFs referring to FIG. 2, β -CD NFs with a specific surface area of 150m calculated by a BET theoretical model2g-1The pore size distribution peaks of β -CD NFs calculated by a BJH model are mostly distributed within 20nm, which indicates that a mesoporous structure is formed on the material.
EXAMPLE 2 preparation of β -CD NFs modified Cotton Fabric Synthesis
(1) 0.1g of β -CD-Cu MOF NFs prepared in the step (1) of 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 β -CD-Cu MOF NFs modified cotton fabric can be obtained.
(2) Under the argon atmosphere, 2.4g of 2,4-TDI and 2 drops (about 100 mu L) of dibutyl tin dilaurate are dissolved in 80mL of anhydrous DMF, about thirty pieces of β -CD-Cu MOF NFs modified cotton fabrics with the diameter of 7cm and the thickness of about 1mm are added, the temperature is raised to 75 ℃, stirring reaction is carried out for 48 hours, then the cotton fabrics are taken out and soaked and washed twice in DMF, diluted hydrochloric acid (0.1M) and water respectively, and the β -CD NFs modified cotton fabrics can be obtained.
The obtained β -CD NFs modified cotton fabric has an electron microscope characterization picture referring to FIG. 3, wherein β -CD-Cu MOFNFs, β -CD-Cu MOF NFs after cross-linking reaction and β -CD NFs are all nano fibrous structures with the length of about 5-10 mu L and the width of about 200nm as shown in FIGS. 3a-3c, and FIGS. 3d-3f and 3g-3i are electron microscope characterization pictures and object pictures of the cotton fabric before and after material modification respectively, and the result shows that β -CD NFs are successfully modified on the cotton fabric.
Example 3: adsorption experiment of bisphenol contaminants
(1) 0.10g of the prepared β -CD NFs was added to a conical flask containing 50mL of water, uniformly dispersed by sonication, 50mL of a 0.2mM solution of bisphenol A (bisphenol B, bisphenol F or bisphenol S) (final concentration of β -CD NFs in solution: 1mg/mL), placed in a water bath at 25 ℃ and magnetically stirred (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 shows a) a graph of the adsorption efficiency of β -CD NFs for bisphenol A (BPA), bisphenol B (BPB), bisphenol F (BPF) and bisphenol S (BPS) as a function of time, b) the adsorption efficiency of β -CD NFs for BPA, BPB, BPF and BPS when equilibrium adsorption is reached.
FIG. 5 is a Langmuir adsorption isotherm of β -CD NFs versus BPA a), BPB b), BPF c) and BPS d).
(2) The adsorption result shows that after the β -CD NFs are adsorbed, the concentrations of four bisphenol pollutants are greatly reduced, particularly for bisphenol A and bisphenol B, the adsorption rates of the materials to the bisphenol A and the bisphenol B can reach higher than 99% when the dosage of β -CD NFs is 1mg/mL and the initial concentration of the pollutants is 0.1mM under the condition of 25 ℃, the adsorption rates of β -CD NFs to bisphenol F and bisphenol S can also reach 94% and 92% respectively (figure 4) under the same condition, the adsorption binding constant (K) of β -CD NFs to bisphenol A calculated by a Langmuir isothermal adsorption equation at the dosage of β -CD NFs and the temperature of 25 ℃ can reach as high as 105L/mol, higher than that of the β -CD polymer water purification and adsorption material (figure 5).
Example 4 adsorption experiment of a simple Water purifier using β -CD NFs-modified Cotton Fabric as an adsorbent Material on bisphenol contaminants in Drinking Water
The adsorption material in the commercial activated carbon water purifier is taken out, β -CD NFs modified cotton fabric is placed into the adsorption material, quartz sand serving as a supporting material is placed into the cotton fabric to be alternately stacked with the cotton fabric, and the simple water purifier is prepared.
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 diphenol 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 can be made without departing from the scope of the invention.
Claims (10)
1. A porous β -cyclodextrin cross-linked polymer nanofiber is characterized in that β -cyclodextrin-copper metal organic framework nano materials are used as templates, 2, 4-toluene diisocyanate is used as a cross-linking agent, and the prepared porous β -cyclodextrin cross-linked polymer nanofiber with β -cyclodextrin molecules orderly arranged in a dimer structure is obtained.
2. A method of making the porous β -cyclodextrin cross-linked polymer nanofiber recited in claim 1, comprising the steps of:
(1) using water as a solvent, fully mixing and dissolving β -cyclodextrin, sodium hydroxide and copper chloride dihydrate, filtering to remove insoluble substances, pouring absolute ethyl alcohol into filtrate, washing obtained precipitates with the ethanol, and drying in vacuum to obtain blue solid, namely the β -cyclodextrin-copper metal organic framework template material;
(2) stirring β -cyclodextrin-copper metal organic framework template material and 2, 4-toluene diisocyanate under argon atmosphere by using anhydrous N, N-dimethylformamide as a solvent and dibutyltin dilaurate as a catalyst for reaction, centrifuging a product obtained by the reaction after the reaction is finished, washing the product with N, N-dimethylformamide, and then washing the product with diluted hydrochloric acid and water respectively to obtain the milky porous β -cyclodextrin cross-linked polymer nanofiber.
3. The method for preparing porous β -cyclodextrin cross-linked polymer nanofiber according to claim 2, wherein in step (1), β -cyclodextrin, sodium hydroxide, and copper chloride dihydrate are fed in a molar ratio of 0.005:1: 0.01.
4. The method for preparing the porous β -cyclodextrin cross-linked polymer nanofiber as claimed in claim 2, wherein in step (1), β -cyclodextrin and sodium hydroxide are dissolved in water, and then copper chloride dihydrate aqueous solution is added to mix uniformly.
5. The method for preparing porous β -cyclodextrin cross-linked polymer nanofiber according to claim 2, wherein in step (2), β -cyclodextrin-copper metal organic framework template material and 2, 4-toluene diisocyanate are fed in a mass ratio of 5: 3.
6. The method for preparing porous β -cyclodextrin cross-linked polymer nanofiber according to claim 2, wherein in step (2), β -cyclodextrin-copper metal organic framework template material is dispersed in N, N-dimethylformamide, dibutyltin dilaurate is added and stirred uniformly, and finally 2, 4-toluene diisocyanate is added.
7. The method for preparing porous β -cyclodextrin crosslinked polymer nanofiber according to claim 2, wherein the reaction temperature in step (2) is 75 ℃ and the reaction time is 24 hours.
8. Use of the porous β -cyclodextrin cross-linked polymer nanofiber as claimed in claim 1 for removing bisphenol type organic pollutants in a water body.
9. The use of claim 8, wherein the porous β -cyclodextrin cross-linked polymer nanofiber is modified to cotton fabric to obtain a composite adsorbent material, and then 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 β -cyclodextrin-copper metal organic framework template material in absolute ethyl alcohol, immersing cotton fabric fibers in the anhydrous ethyl alcohol, taking out the cotton fabric fibers, and drying the cotton fabric fibers at room temperature to obtain β -cyclodextrin-copper metal organic framework template material modified cotton fabric;
(2) the 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 β -cyclodextrin-copper metal organic framework template material modified cotton fabric, reacting under the argon atmosphere and mild stirring at 75 ℃ for 48 hours, finally soaking and washing the obtained cotton fabric in N, N-dimethylformamide, diluted hydrochloric acid and water for two times, and obtaining the porous β -cyclodextrin cross-linked polymer nanofiber modified cotton fabric.
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| T.RAJKUMAR等: "Cyclodextrin-metal-organic framework (CD-MOF): From synthesis to applications", 《JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY》 * |
| WENYA HE等: "Porous beta-cyclodextrin nanotubular assemblies enable high-efficiency removal of bisphenol micropollutants from aquatic systems", 《NANO RESEARCH》 * |
| 李阳雪等: "用环糊精的金属有机框架材料作为模板制备多孔有机笼", 《化学学报》 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112062955A (en) * | 2020-09-07 | 2020-12-11 | 南方科技大学 | Naphthalene tube-based reticular polymer and application thereof in drinking water purification |
| CN112062955B (en) * | 2020-09-07 | 2022-07-05 | 南方科技大学 | Naphthalene tube-based reticular polymer and application thereof in drinking water purification |
| CN113522362A (en) * | 2021-06-16 | 2021-10-22 | 南京理工大学 | Metal organic framework nano CuO composite material and preparation method thereof |
| WO2023223787A1 (en) * | 2022-05-17 | 2023-11-23 | リンテック株式会社 | Adhesive composition, adhesive, adhesive sheet, display body, and repeated bending device |
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| Publication number | Publication date |
|---|---|
| CN111203199B (en) | 2020-12-11 |
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