A γ-cyclodextrin two-dimensional porous organic polymer, its preparation method and application

Abstract

The present invention discloses a γ-cyclodextrin two-dimensional porous organic polymer, a preparation method thereof and an application thereof. By means of a strategy for regulating the mass transfer efficiency and reaction efficiency in an ion-regulated crystallization polymerization reaction, problems such as the directional polymerization of the selective alignment of the x and y crystal axes and the controllable restricted polymerization of the z axis in the process of a crystalline three-dimensional crosslinking reaction are solved, and the construction of ordered pores and the control of the two-dimensional morphology of the polymerization product of γ-cyclodextrin in the crystalline three-dimensional crosslinking reaction are realized. The γ-cyclodextrin two-dimensional porous organic polymer prepared by the method has the advantages of uniform thickness and precise regulation, good dispersibility, high thermal stability, ordered porous structure, etc., and retains the host-guest chemical properties of cyclodextrin, and can be applied to fields such as catalyst loading, adsorption separation, drug slow release, etc.

Description

Technical Field

[0001] The present invention relates to the field of preparation of two-dimensional porous organic polymer materials, and particularly to a method for preparing a two-dimensional porous organic polymer based on cyclodextrin. Technical Background

[0002] Two-dimensional porous organic polymers (2D-POPs) are covalently bonded organic porous materials with a nanoscale thickness. Their porous structures have unique advantages in terms of flexibility and accessibility, and thus show promising prospects in many fields such as gas storage and separation, optoelectronics, proton conduction, heterogeneous catalysis, removal of micro-pollutants, energy storage and conversion. The synthesis of 2D-POPs usually relies on two-dimensional molecular structures, and the reversible synthesis strategy is its traditional synthesis method. Its products have a two-dimensional crystalline porous network structure connected by reversible covalent bonds, and their stacking in the third dimension only depends on the non-covalent intermolecular interactions between two-dimensional covalent network layers. The ultrathin materials obtained through subsequent cumbersome exfoliation are usually fragmented, so their chemical and mechanical stabilities are limited, and thickness control and post-modification are even more difficult. Polymers with a three-dimensional cross-linked structure constructed by irreversible covalent bonds have advantages in terms of stability. At the same time, the construction of an ordered porous structure can be achieved by polymerization on the basis of pre-assembly of monomers. However, the result of cross-linking the crystals is usually to transform the entire crystal particles or random fragments into gels, because there is still a lack of effective strategies to obtain polymers with a two-dimensional morphology through three-dimensional irreversible cross-linking of crystals. Therefore, it is of great significance to develop a new strategy for controlling irreversible cross-linking of crystals, that is, to achieve precise positioning in two dimensions and controllable constraints in three dimensions.

[0003] Cyclodextrin (CD) is a natural macrocyclic molecule composed of sugar groups with a hydrophobic cavity, having molecular recognition and complexation characteristics, and is of great significance to host-guest / supramolecular chemistry. The polymerization of CD has been achieved through various synthetic routes of irreversible hydroxyl cross-linking. Due to its unique hierarchical porosity, it has excellent performance in the fields of adsorption separation and heterogeneous catalysis, but the synthesis of two-dimensional CD-based porous organic polymers (2D-CD-POPs) is still a challenge, especially for polymers with an irreversible three-dimensional cross-linked structure and the ordered orientation of their macrocyclic building units. Summary of the Invention

[0004] The object of the present invention is to provide a method for preparing a two-dimensional porous organic polymer based on γ-cyclodextrin in view of the problems existing in the above-mentioned prior art. This preparation method has the advantages of simple steps and low cost. The obtained γ-cyclodextrin two-dimensional porous organic polymer has the advantages of uniform and precisely adjustable thickness, good dispersibility, high thermal stability, and ordered porous structure.

[0005] A γ-cyclodextrin two-dimensional porous organic polymer provided by the present invention is characterized in that: using natural macrocyclic molecule γ-cyclodextrin as the monomer for the polymerization reaction, first, γ-cyclodextrin obtains an ordered pre-assembly with a porous structure through the crystallization arrangement in the framework structure; then, using a monomer containing an epoxy group as the cross-linking agent, by regulating the difference in solvation effects in the confined space, the mass transfer efficiency and reaction efficiency of the cross-linking agent in the pores are differentiated, and further the crystal axis differentiation of the polymerization reaction inside the crystal is realized, so as to prepare an orderly arranged γ-cyclodextrin two-dimensional porous organic polymer.

[0006] The preparation method of the γ-cyclodextrin two-dimensional porous organic polymer described in the present invention specifically includes the following steps:

[0007] Step 1: Synthesis of γ-CD-MOF crystals

[0008] Fully mix γ-CD and potassium salt and dissolve them in water, add methanol to the obtained solution, and then place it in an oven for heating and growth. After the obtained crystals are dried in vacuum, a white solid is obtained, which is the γ-cyclodextrin metal-organic framework template material, denoted as γ-CD-MOF.

[0009] Step 2: Synthesis of γ-cyclodextrin two-dimensional porous organic polymer

[0010] Using a mixed solvent of ethanol - methanol - acetone - acetonitrile - isopropanol as the reaction solvent and a monomer containing an epoxy group as the cross-linking agent, react γ-CD-MOF and the cross-linking agent under heating conditions; after the reaction is completed, centrifuge the reaction product (denoted as CL-CD-MOF), and ultrasonically disperse it in water to obtain the γ-cyclodextrin two-dimensional porous organic polymer, denoted as 2D-CD-POPs.

[0011] Preferably, in step 1, the potassium salt is at least one of anhydrous potassium phosphate, monopotassium phosphate, dipotassium hydrogen phosphate, anhydrous potassium bicarbonate, and anhydrous potassium carbonate.

[0012] Preferably, in step 1, the potassium salt and γ-CD are fed in a molar ratio of 2 - 70:1.

[0013] Preferably, in step 1, the potassium salt and γ-CD are dissolved in water, and the concentration of the potassium salt is 0.1 - 1.0 M.

[0014] Preferably, in step 1, the potassium salt and γ-CD are first dissolved in water, and then methanol is added. The dosage ratio of the potassium salt to methanol is 0.1 - 5 g:0 - 5 mL.

[0015] Preferably, in step 1, the temperature for heating and growth is 20 - 80 °C, and the growth time is 0.5 - 10 d.

[0016] Preferably, the volume ratio of ethanol, methanol, acetone, acetonitrile, and isopropanol in the reaction solvent described in step 2 is 1-3: 1-3: 0-3: 0-3: 0-3.

[0017] Preferably, in step 2, the crosslinking agent includes at least one of crosslinking agents containing two or more epoxy groups such as ethylene glycol diglycidyl ether, butanediol diglycidyl ether, hexanediol diglycidyl ether, and glycerol triglycidyl ether.

[0018] Preferably, in step 2, the crosslinking agent and γ-CD-MOF are fed in a mass ratio of 1-60:1.

[0019] Preferably, in step 2, the dosage ratio of γ-CD-MOF to the reaction solvent is 20-600 mg: 10 mL.

[0020] Preferably, in step 2, γ-CD-MOF and the crosslinking agent are reacted under heating conditions of 30-100 °C, and the reaction time is 0.5-7 d.

[0021] The present invention further provides several applications of the γ-cyclodextrin two-dimensional porous organic polymer:

[0022] Application 1: Used as a carrier to load metal nanoparticles to prepare a composite catalyst material for catalyzing C-C cross-coupling reactions or selective C-H activation reactions.

[0023] Furthermore, the composite catalyst material can be prepared by the following method:

[0024] Dissolve the metal compound in an organic solvent, then add the γ-cyclodextrin two-dimensional porous organic polymer for sufficient adsorption; after the adsorption is completed, reduce the metal compound with a reducing agent to obtain the γ-cyclodextrin two-dimensional porous organic polymer loaded with metal nanoparticles.

[0025] The metal compound described in the above steps can be a palladium- or gold-containing substance such as potassium tetrachloropalladate, potassium hexachloropalladate, palladium acetate, and sodium chloroaurate.

[0026] The mass ratio of the metal compound and 2D-CD-POPs described in the above steps is 1: 10-60.

[0027] The organic solvent described in the above steps is a mixture of dichloromethane and methanol, and its volume ratio is 1-3: 0-3.

[0028] The reducing agent described in the above steps is a hydride reducing agent such as sodium borohydride and lithium aluminum hydride.

[0029] Application 2: Used as an adsorbent to remove organic pollutants such as bisphenol A and hormones in water.

[0030] Application 3: Used as a carrier to load drugs and achieve sustained release of drugs. The following method can be specifically adopted:

[0031] Disperse 2D-CD-POPs and drugs in a mixed solution of ultrapure water and ethanol. After stirring and reacting in the dark, distill off ethanol under reduced pressure. Centrifuge the remaining aqueous solution, collect the supernatant, filter it, and then freeze-dry it. The obtained powder is the drug-loaded γ-cyclodextrin two-dimensional porous organic polymer.

[0032] The drugs in the above steps include prednisone, tretinoin, potassium 4-methoxysalicylate, niacinamide, copper tripeptide, biotin tripeptide, etc.

[0033] In the above steps, the mass ratio of 2D-CD-POPs to drugs is 1-5:1.

[0034] In the above steps, the volume ratio of ultrapure water to ethanol is 1:1-3.

[0035] Compared with the prior art, the beneficial effects of the present invention are reflected in:

[0036] The present invention provides a new synthesis strategy for carrying out three-dimensional irreversible cross-linking reactions under the condition of monomeric crystalline order pre-organization to obtain an ordered porous polymer material with a two-dimensional morphology, solving the problems of selective alignment polymerization of the x and y crystal axes and restricted polymerization of the z axis during the crystalline three-dimensional cross-linking reaction. The γ-cyclodextrin two-dimensional porous organic polymer prepared by the method of the present invention has the advantages of uniform and precisely adjustable thickness, good dispersibility, high thermal stability, ordered porous structure, etc., and retains the host-guest chemical properties of cyclodextrin, and can be effectively applied in the fields of catalysis, adsorption separation, drug loading and sustained release, etc. Description of the Drawings

[0037] Figure 1 It is the crystal diagram of the γ-CD-MOF prepared in Example 1 of the invention. In the figure, (a) and (b) correspond to the x / y and z axis directions respectively.

[0038] Figure 2 It is the SEM diagram, AFM diagram and thickness curve of the 2D-CD-POPs prepared in Example 1 of the invention.

[0039] Figure 3 It is the SEM diagram, AFM diagram and thickness curve of the 2D-CD-POPs prepared in Example 2 of the invention.

[0040] Figure 4 It is the SEM diagram, AFM diagram and thickness curve of the 2D-CD-POPs prepared in Example 3 of the invention.

[0041] Figure 5SEM image, AFM image and thickness curve of 2D-CD-POPs prepared for Invention Example 4.

[0042] Figure 6 Nitrogen adsorption-desorption isotherm curve and pore size distribution diagram of 2D-CD-POPs prepared for Invention Example 1.

[0043] Figure 7 Infrared spectra of γ-CD-MOF and 2D-CD-POPs prepared for Invention Example 1.

[0044] Figure 8 Thermogravimetric curve of 2D-CD-POPs prepared for Invention Example 1.

[0045] Figure 9 Transmission electron microscope image of Pd@2D-CD-POPs prepared for Invention Example 5.

[0046] Figure 10 Catalytic efficiency curve of Pd@2D-CD-POPs prepared for Invention Example 5.

[0047] Figure 11 Adsorption effect curve of 2D-CD-POPs on different organic pollutants in Invention Example 6.

[0048] Figure 12 Sustained release curve of 2D-CD-POPs loaded with different drugs in Invention Example 7. Detailed implementation manners

[0049] The present invention will be further described below with reference to the accompanying drawings and embodiments.

[0050] I. Preparation of γ-cyclodextrin two-dimensional porous organic polymer

[0051] Example 1

[0052] The γ-cyclodextrin two-dimensional porous organic polymer is prepared according to the following steps:

[0053] Step 1: Synthesis of γ-CD-MOF crystals

[0054] 1 mmol of γ-CD and 10 mmol of anhydrous potassium carbonate are fully mixed and dissolved in 30 mL of deionized water, 3 mL of methanol is added, and the resulting solution is placed in an oven at 30 °C for 7 days; the obtained crystals are dried in vacuo to obtain a white solid, which is the γ-cyclodextrin metal-organic framework template material (γ-CD-MOF).

[0055] Step 2: Synthesis of γ-cyclodextrin two-dimensional porous organic polymer

[0056] Disperse 100 mg of γ-CD-MOF crystals in 10 mL of a reaction solvent (a mixture of ethanol, methanol, acetone, and acetonitrile in a volume ratio of 1:1:1:1). After adding 2 g of ethylene glycol diglycidyl ether and mixing evenly, heat the resulting mixture at 50 °C for 5 days. The obtained product (denoted as CL-CD-MOF) is ultrasonically dispersed in water and then vacuum dried to obtain γ-cyclodextrin two-dimensional porous organic polymer (2D-CD-POPs).

[0057] Example 2

[0058] Step 1: Synthesis of γ-CD-MOF crystals

[0059] Fully mix and dissolve 1 mmol of γ-CD and 10 mmol of anhydrous potassium carbonate in 30 mL of deionized water. Add 3 mL of methanol, and place the resulting solution in an oven at 30 °C for 7 days. The obtained crystals are vacuum dried to obtain a white solid, which is the γ-cyclodextrin metal-organic framework template material (γ-CD-MOF).

[0060] Step 2: Synthesis of γ-cyclodextrin two-dimensional porous organic polymer

[0061] Disperse 100 mg of γ-CD-MOF crystals in 10 mL of a reaction solvent (a mixture of ethanol, methanol, acetone, and acetonitrile in a volume ratio of 2:1:1:1). After adding 2 g of ethylene glycol diglycidyl ether and mixing evenly, heat the resulting mixture at 50 °C for 5 days. The obtained product (denoted as CL-CD-MOF) is ultrasonically dispersed in water and then vacuum dried to obtain γ-cyclodextrin two-dimensional porous organic polymer (2D-CD-POPs).

[0062] Example 3

[0063] Step 1: Synthesis of γ-CD-MOF crystals

[0064] Fully mix and dissolve 1 mmol of γ-CD and 10 mmol of anhydrous potassium carbonate in 30 mL of deionized water. Add 3 mL of methanol, and place the resulting solution in an oven at 30 °C for 7 days. The obtained crystals are vacuum dried to obtain a white solid, which is the γ-cyclodextrin metal-organic framework template material (γ-CD-MOF).

[0065] Step 2: Synthesis of γ-cyclodextrin two-dimensional porous organic polymer

[0066] Disperse 100 mg of γ-CD-MOF crystals in 10 mL of reaction solvent (a mixture of ethanol, methanol, acetone, and acetonitrile in a volume ratio of 2:1:2:1). After adding 2 g of ethylene glycol diglycidyl ether and mixing evenly, heat the resulting mixture at 50 °C for 5 days. The obtained product (denoted as CL-CD-MOF) is ultrasonically dispersed in water and then vacuum dried to obtain γ-cyclodextrin two-dimensional porous organic polymer (2D-CD-POPs).

[0067] Example 4

[0068] Step 1: Synthesis of γ-CD-MOF crystals

[0069] Fully mix 1 mmol of γ-CD and 10 mmol of anhydrous potassium carbonate and dissolve them in 30 mL of deionized water. Add 3 mL of methanol, and place the resulting solution in an oven at 30 °C for 7 days; the obtained crystals are vacuum dried to obtain a white solid, which is the γ-cyclodextrin metal-organic framework template material (γ-CD-MOF).

[0070] Step 2: Synthesis of γ-cyclodextrin two-dimensional porous organic polymer

[0071] Disperse 100 mg of γ-CD-MOF crystals in 10 mL of reaction solvent (a mixture of ethanol, methanol, isopropanol, and acetonitrile in a volume ratio of 2:1:1:1). After adding 2 g of ethylene glycol diglycidyl ether and mixing evenly, heat the resulting mixture at 50 °C for 5 days. The obtained product (denoted as CL-CD-MOF) is ultrasonically dispersed in water and then vacuum dried to obtain γ-cyclodextrin two-dimensional porous organic polymer (2D-CD-POPs).

[0072] The single crystal structure of the γ-CD-MOF prepared in Example 1 is as Figure 1 shown, Figure 1 a and b are views in the x / y-axis and z-axis directions respectively, revealing that the K + ions in CD-MOF exist in a ratio of 2:1 relative to γ-CD and are connected by coordination bonds.

[0073] The scanning electron microscope and atomic force microscope images of the 2D-CD-POPs prepared in Example 1 are as Figure 2 shown. It can be seen that the product exhibits a two-dimensional sheet-like morphology, with a size of 10 - 20 μm and a thickness of 600 nm.

[0074] The scanning electron microscope and atomic force microscope images of the 2D-CD-POPs prepared in Example 2 are as Figure 3 shown. It can be seen that the thickness of the product is 35 nm, and the size remains unchanged compared to Example 1.

[0075] The scanning electron microscope and atomic force microscope images of the 2D-CD-POPs prepared in Example 3 are as follows Figure 4 shown. It can be seen that the product thickness is 20 nm and the size remains unchanged compared to Example 1.

[0076] The scanning electron microscope and atomic force microscope images of the 2D-CD-POPs prepared in Example 4 are as follows Figure 5 shown. It can be seen that the product thickness is 3 nm and the size remains unchanged compared to Example 1.

[0077] Combined with Figure 2 , 3 , 4, and 5, it shows that the thickness can be regulated by changing the solvent ratio, achieving selective polymerization along the x and y crystal axes and restricted polymerization along the z axis.

[0078] The nitrogen adsorption-desorption isotherm curve and pore size distribution diagram of the 2D-CD-POPs prepared in Example 1 are as follows Figure 6 shown. The specific surface area of the 2D-CD-POPs is 3.5 m 2 g -1 . Calculated from the DFT model, the pore size distribution of the 2D-CD-POPs is around 5 nm, indicating that a mesoporous structure has formed on the material.

[0079] The Fourier transform infrared spectroscopy diagrams of the γ-CD-MOF and 2D-CD-POPs prepared in Example 1 are as follows Figure 7 shown. The changes in the peaks at 2870 - 2920 cm -1 and 1020 - 1150 cm -1 in the infrared spectra indicate that a crosslinking reaction has occurred.

[0080] The thermogravimetric curve of the 2D-CD-POPs prepared in Example 1 is as follows Figure 8 shown. The pyrolysis temperature of the 2D-CD-POPs is 380 °C, indicating that the crosslinking reaction has improved the thermal stability and structural stability of the γ-CD material (whose pyrolysis temperature is 280 °C).

[0081] II. Applications of γ-cyclodextrin two-dimensional porous organic polymers

[0082] Example 5

[0083] In this example, the γ-cyclodextrin two-dimensional porous organic polymer loaded with palladium nanoparticles is prepared according to the following steps:

[0084] Dissolve 4 mg of palladium acetate in a solvent composed of dichloromethane and methanol in a volume ratio of 1:1. After uniform dispersion, add 200 mg of the 2D-CD-POPs prepared in Example 3 and adsorb at room temperature for 24 h. After the adsorption is completed, add 3 mL of methanol solution containing 2 mg of sodium borohydride and stir at room temperature for 3 h to reduce palladium ions to palladium nanoparticles. Dry to obtain γ-cyclodextrin two-dimensional porous organic polymer loaded with palladium nanoparticles (denoted as Pd@2D-CD-POPs). The transmission electron microscope of the Pd@2D-CD-POPs prepared in this example is as Figure 9 shown, where the particle size of the palladium metal particles is 3 nm.

[0085] Application of Pd@2D-CD-POPs as a catalyst for C-C cross-coupling reaction: Add 37 mg of phenylboronic acid and 32 mg of bromobenzene to a 20 mL glass bottle containing 5 mL of absolute ethanol, then add 10 mg of Pd@2D-CD-POPs, disperse uniformly by ultrasound, place the glass bottle at 30 °C, and stir magnetically (300 r / min). Terminate the reaction at different time points, filter the reaction solution, separate the product, and finally dry to calculate the yield. The catalytic efficiency curve diagram is as Figure 10 shown, and the catalysis can be completed in 30 min with a conversion rate of 100%.

[0086] Example 6

[0087] Adsorption experiment of 2D-CD-POPs on different organic pollutants:

[0088] Add 20 mg of 2D-CD-POPs to a 50 mL beaker, and respectively add 20 mL of aqueous solutions of different organic pollutants (bisphenol A, bisphenol F, bisphenol S or bisphenol B) with a concentration of 0.2 mM (the final concentration of 2D-CD-POPs in the solution is 1 mg / mL). Place the beaker at 30 °C and stir magnetically (500 r / min) for 2 h. Take out 1 mL of the above solution at different time points, filter, and measure the absorbance with a UV-visible spectrophotometer at the maximum absorption wavelength of the bisphenol compound to determine the pollutant concentration in the adsorbed solution, so as to calculate the adsorption amount and adsorption efficiency.

[0089] In this example, the adsorption efficiency change diagram of 2D-CD-POPs for bisphenol A (BPA), bisphenol B (BPB), bisphenol F (BPF) and bisphenol S (BPS) with time is as Figure 11 shown, and the adsorption occurs instantaneously. Especially, BPA reaches 97% adsorption within 30 s.

[0090] Example 7

[0091] Drug loading and slow release experiment of 2D-CD-POPs:

[0092] 50 mg of the 2D-CD-POPs prepared in Example 3 and 14 mg of different drugs (prednisone, retinoic acid, potassium 4-methoxysalicylate, niacinamide, GHK-Cu or Biotin-GHK) were separately added into a 50 mL round-bottom flask, and 10 mL of a mixed solvent composed of ultrapure water and ethanol in a volume ratio of 1:1 was added. The reaction was stirred under light protection at 30 °C for 24 h. After the reaction, ethanol was removed by distillation under reduced pressure. The remaining aqueous solution was centrifuged and the supernatant was collected, filtered and freeze-dried. The obtained powder was the γ-cyclodextrin two-dimensional porous organic polymer loaded with the drug.

[0093] 50 mg of the drug-loaded 2D-CD-POPs prepared above was added into a 50 mL beaker, 20 mL of normal saline was added, and after being dispersed evenly, a drug release experiment was carried out at 37 °C. 1 mL of the above solution was taken out at different time points, filtered, and the absorbance was measured with a UV-visible spectrophotometer at the maximum absorption wavelength of the drug to determine the drug concentration in the released solution, so as to calculate the release amount.

[0094] In this example, the sustained release curves of 2D-CD-POPs loaded with prednisone (PDN), retinoic acid (VA), potassium 4-methoxysalicylate (MSK), niacinamide (NR), GHK-Cu, and Biotin-GHK are as Figure 12 shown, especially the cumulative release amount of Biotin-GHK is only 63% within 68 h.

[0095] The above are only exemplary embodiments of the present invention and are not intended to limit the present invention. Any modifications, equivalent replacements, improvements, etc. made within the spirit and principle of the present invention shall be included within the protection scope of the present invention.

Claims

1. A γ-cyclodextrin two-dimensional porous organic polymer, characterized in that: Using the natural macrocyclic molecule γ-cyclodextrin as the monomer of the polymerization reaction, first, γ-cyclodextrin is obtained with an ordered pre-assembly having a porous structure through the crystallization arrangement in the framework structure; then, a monomer containing an epoxy group is used as the cross-linking agent, and by regulating the difference in solvation effects within the confined space, the mass transfer efficiency and reaction efficiency of the cross-linking agent within the pores are differentiated, and further, the crystal axis differentiation of the polymerization reaction within the crystal is achieved, thereby preparing an orderly arranged two-dimensional porous organic polymer of γ-cyclodextrin; the preparation method of the two-dimensional porous organic polymer of γ-cyclodextrin includes the following steps: Step 1: Synthesis of γ-CD-MOF crystals γ-CD and anhydrous potassium carbonate are fully mixed and dissolved in water, methanol is added to the resulting solution, and then it is placed in an oven for heating and growth. The obtained crystals are vacuum dried to obtain a white solid, which is the γ-cyclodextrin metal-organic framework template material γ-CD-MOF crystals; wherein, the potassium salt and γ-CD are fed in a molar ratio of 2 to 70:

1. Step 2: Synthesis of two-dimensional porous organic polymer of γ-cyclodextrin Using a mixed solvent as the reaction solvent and a monomer containing an epoxy group as the cross-linking agent, γ-CD-MOF and the cross-linking agent ethylene glycol diglycidyl ether are reacted under heating conditions; after the reaction is completed, the reaction product CL-CD-MOF is centrifuged and ultrasonically dispersed in water to obtain the two-dimensional porous organic polymer of γ-cyclodextrin 2D-CD-POPs; wherein: the cross-linking agent and γ-CD-MOF are fed in a mass ratio of 1 to 60:1; the mixed solvent is composed of ethanol, methanol, acetone, and acetonitrile in a volume ratio of 1 to 3:1 to 3:1 to 3:1 to 3, or is composed of ethanol, methanol, acetonitrile, and isopropanol in a volume ratio of 2 to 3:1 to 3:1 to 3:1 to 3.

2. The γ-cyclodextrin two-dimensional porous organic polymer according to claim 1, wherein: In Step 1, the temperature of the heating growth is 20 to 80 °C, and the growth time is 0.5 to 10 d.

3. The preparation method of the γ-cyclodextrin two-dimensional porous organic polymer according to claim 1, wherein: In Step 2, the dosage ratio of γ-CD-MOF to the reaction solvent is 20 to 600 mg:10 mL.

4. The preparation method of the γ-cyclodextrin two-dimensional porous organic polymer according to claim 1, characterized in that: In Step 2, γ-CD-MOF and the cross-linking agent are reacted under heating conditions at 30 to 100 °C, and the reaction time is 0.5 to 7 d.

5. Use of the γ-cyclodextrin two-dimensional porous organic polymer according to claim 1, characterized in that: It is used as a carrier to load metal nanoparticles to prepare a composite catalyst material for catalyzing C-C cross-coupling reactions or selective C-H activation reactions; Or, it is used as an adsorbent to remove organic pollutants in water; Or, it is used as a carrier to load drugs to achieve the slow release of drugs.

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