阅读说明：本技术 腺嘌呤及柠檬酸与Zn2+构筑的MOFs材料及其制备方法 (Adenine and citric acid with Zn2+Constructed MOFs material and preparation method thereof ) 是由 李峻峰 陈洁琼 宋联荣 王廷丽 罗昆 王皓 王立 张佩聪 于 2020-12-11 设计创作，主要内容包括：本发明提供了腺嘌呤及柠檬酸与Zn～(2+)构筑的MOFs材料及其制备方法,属于金属有机框架材料技术领域。腺嘌呤及柠檬酸与Zn～(2+)构筑的MOFs材料的结晶性好,晶粒尺寸在0.1μm～20μm,BJH法最可几孔径为3nm。该MOFs材料的制备方法是将锌盐、腺嘌呤、柠檬酸三钠分别溶于溶剂中混合配制原液,再按照Zn～(2+)离子:腺嘌呤:柠檬酸的物质的量比为(1.5～3.5)mol:(0.6～1.2)mol:(1～2.5)mol将原液混合后密闭反应,得到新型结构的金属有机框架材料。本发明通过引入柠檬酸作第二配体协同腺嘌呤,可以实现MOF结构的调节,且该材料兼具生物相容性和适宜孔径。(The invention provides adenine, citric acid and Zn 2+ The constructed MOFs material and the preparation method thereof belong to the technical field of metal organic framework materials. Adenine and citric acid with Zn 2+ The crystallinity of the constructed MOFs material is good, the grain size is 0.1-20 μm, and the maximum aperture of the BJH method is 3 nm. The preparation method of the MOFs material comprises the steps of respectively dissolving zinc salt, adenine and trisodium citrate in a solvent, mixing to prepare a stock solution, and then mixing according to Zn 2+ And mixing the stock solution according to the mass ratio of the ions adenine to citric acid of (1.5-3.5) mol to (0.6-1.2) mol to (1-2.5) mol, and carrying out closed reaction to obtain the metal organic framework material with the novel structure. According to the invention, citric acid is introduced as a second ligand to cooperate with adenine, so that the regulation of the MOF structure can be realized, and the material has biocompatibility and a proper pore size.)

1. Adenine and citric acid with Zn²⁺The constructed MOFs material is characterized by comprising the following components: with Zn²⁺As central ion, adenine as main ligand and citric acid as secondary ligand.

2. Adenine and citric acid as in claim 1 and Zn²⁺Constructed MOFs materials characterized by Zn²⁺The amount ratio of the ions adenine and citric acid is (1.5-3.5) mol, (0.6-1.2) mol, (1-2.5) mol.

3. Adenine and citric acid as in claim 1 and Zn²⁺The constructed MOFs material is characterized by good crystallinity, the grain size is 0.1-20 μm, and the maximum probable pore diameter of the BJH method is 3 nm.

4. Adenine and citric acid as in claim 1 and Zn²⁺The preparation method of the constructed MOFs material is characterized by comprising the following steps:

(1) weighing 0.15-0.35 g of adenine, dissolving the adenine in 5-35 mL of organic solvent to obtain a solution A with the concentration of 0.03-0.08 mol/L, weighing 0.65-1.35 g of trisodium citrate, dissolving the trisodium citrate in 3-15 mL of deionized water to obtain a solution B with the concentration of 0.1-0.6 mol/L, weighing 0.45-1.20 g of zinc salt, dissolving the zinc salt in 10-35 mL of organic solvent to obtain a solution C with the concentration of 0.03-0.28 mol/L;

(2) measuring 5-30 mL of solution A and 3-15 mL of solution B, mixing, adding 5-15 mL of ethanol and 1-5 mL of H₂O to obtain a solution D;

(3) weighing 10-30 mL of the solution C, mixing the solution C with the solution D obtained in the step (2), and stirring the mixture for 10-15 s by using a glass rod to obtain a uniform reaction solution;

(4) transferring the reaction liquid obtained in the step (3) into a polytetrafluoroethylene lining reaction kettle to perform closed reaction for 24-48 hours at the temperature of 90-130 ℃;

(5) and cooling to room temperature after the reaction is finished, separating to obtain a precipitate, washing for 3-5 times by using N, N-2-methylformamide, washing for 3-5 times by using absolute ethyl alcohol, and drying for 5-10 hours at the temperature of 100-170 ℃ to obtain a product.

5. Adenine and citric acid as in claim 4 and Zn²⁺The preparation method of the constructed MOFs material is characterized by comprising the following steps: the organic solvent in the step (1) is N, N-2-methylformamide or dimethyl sulfoxide, and preferably N, N-2-methylformamide.

6. Adenine and citric acid as in claim 4 and Zn²⁺The preparation method of the constructed MOFs material is characterized by comprising the following steps: the zinc salt in the step (1) is zinc acetate or zinc nitrate, preferably zinc acetate.

Technical Field

The invention belongs to the technical field of metal organic framework materials, and relates to adenine, citric acid and Zn²⁺Constructed MOFs materials and a preparation method thereof.

Background

The metal organic frameworks (also called porous co-polymers, MOFs) are a new type of crystalline porous material, and are one of the hot spots of material research in recent years due to their unique properties and broad application prospects. The material is constructed by organic ligands and inorganic metal units, an extended and regular network structure is formed by metal ions/clusters and organic connectors through coordination bonds, so that a highly functionalized pore space is generated in crystal lattices, and the material has the characteristics of high porosity, low density, large specific surface area, regular pore channels, adjustable pore diameter, diversity of topological structures and the like, and is widely applied to the fields of gas adsorption, separation, purification, storage, sensing, catalysis and the like.

Regarding the application of MOFs in the biological field, the number of classes is known to be small, most of the existing MOF structures use organic matters containing benzene rings as ligands, and biomolecules are rarely introduced, so that the MOF structures are poor in biocompatibility and are less applied in the biological field. Research shows that the nucleobase has rich self-assembly characteristic and may be used in structure assembly and function design of coordination polymer. The application of nucleobases as organic linkers has significant features and allows the construction of a wide variety of bioMOFs. Adenine is used as a component of human nucleic acid, and has good biocompatibility; meanwhile, the adenine is used as a rigid ligand, so that the stability of the material can be greatly improved; in addition, adenine has multiple coordination sites, providing multiple possibilities for MOF structures. However, because adenine has low symmetry, it is difficult to obtain a material with more symmetry and larger pores, so it is considered that the symmetry of the material can be improved by introducing a second ligand with high symmetry. Jihyun An et al synthesized Bio-MOF-1(An J, Geib S J, Rosi N L.Caption-triggered drug release from a pore zinc-adenate metallic-organic frame, 2009,131(24):8376-7.) with adenine as the primary ligand, using diphenic acid as the second ligandLigand, zinc ion as central ion, specific surface of material up to 1700m²Per g, over Na⁺Triggering the release of procainamide. Although the specific surface area of the material is large, the release of the drug responds to the triggering of cations, but the introduction of the biphenyldicarboxylic acid has certain influence on the biocompatibility of the material, and may bring potential risks to the application of the material in organisms. Li Jianrong and the like synthesize an MOF structure (Li Jianrong, Wang Luo, Zhang Peng Dan, and the like) with copper ions as central ions, adenine as a main ligand and glutaric acid as a second ligand, and preparation and application of a microporous Cu-MOF metal organic framework material constructed by adenine and auxiliary ligands [ P]CN110922606A,2020-03-27.), the synthesized metal organic framework has good stability, and the MOF has potential application in the storage and separation of low carbon hydrocarbon gases. Although Cu has the function of sterilization, according to the research of nutrition and food hygiene, the maximum value of the average daily intake of copper element of an adult is 8mg, compared with the maximum value of the average daily intake of zinc element of 40mg, which is 5 times of the maximum value of the copper element. In order to solve the above biocompatibility problem and ensure the stability of the MOF structure, it is necessary to select a ligand and a central ion which are more friendly to living organisms to construct a metal organic framework structure.

The citric acid is edible acid, can enhance normal metabolism in vivo, and has no harm to human body at proper dosage. Citric acid is added to certain food products to provide a good mouthfeel and appetite-promoting effect, and is used in jams, beverages, cans and candies as permitted in china. The citric acid has good symmetry in structure, and can be used as an auxiliary ligand of adenine to improve the porosity and symmetry of the material. Meanwhile, the zinc element is an essential trace element of a human body, plays an extremely important role in important physiological processes of growth and development, reproductive inheritance, immunity, endocrine and the like of the human body, is called as 'flowers of life', 'marriage and harmonia' by people, and cannot lack the zinc element particularly for growing children.

In conclusion, the invention provides the metal organic framework material which takes adenine as a main ligand, citric acid as a second ligand and zinc ions as central ions, can greatly improve the biocompatibility of the material, provides multiple possibilities for the structure of the material, has good prospects in the field of drug controlled release, and is hopeful to be applied to the aspects of gas adsorption, catalysis and the like.

Disclosure of Invention

In view of the above, the present invention provides a method for preparing adenine, citric acid and Zn with environmental protection, simplicity and low cost²⁺Constructed MOFs materials and a preparation method thereof.

The metal-organic framework material is characterized by using Zn²⁺As central ion, adenine as main ligand and citric acid as secondary ligand; the crystallinity is good, the grain size is 0.1-20 μm, and the maximum pore diameter of BJH method is 3 nm.

The invention also provides a preparation method of the organic metal framework material, which comprises the following steps:

(1) weighing 0.15-0.35 g of adenine, dissolving the adenine in 5-35 mL of organic solvent to obtain a solution A with the concentration of 0.03-0.08 mol/L, weighing 0.65-1.35 g of trisodium citrate, dissolving the trisodium citrate in 2-15 mL of deionized water to obtain a solution B with the concentration of 0.1-0.6 mol/L, and weighing 0.45-1.20 g of zinc salt, dissolving the zinc salt in the organic solvent to obtain a solution C with the concentration of 0.03-0.28 mol/L;

(2) weighing 5-35 mL of solution A and 3-15 mL of solution B, mixing, and adding 5-15 mL of ethanol and 1-5 mL of H2O to obtain solution D;

(3) weighing 10-30 mL of the solution C, mixing the solution C with the solution D obtained in the step (2), and stirring the mixture for 10-15 s by using a glass rod to obtain a uniform reaction solution;

(4) transferring the reaction liquid obtained in the step (3) into a polytetrafluoroethylene lining reaction kettle to perform closed reaction for 24-48 hours at the temperature of 90-130 ℃;

(5) and cooling to room temperature after the reaction is finished, separating to obtain a precipitate, washing with N, N-2-methylformamide for 3-5 times, washing with absolute ethyl alcohol for 3-5 times, and drying at 100-170 ℃ for 5-10 hours to obtain a product.

The zinc salt in the step (1) is zinc acetate or zinc nitrate, preferably zinc acetate.

The organic solvent in step (1) comprises N, N-2-methylformamide or dimethyl sulfoxide, preferably N, N-2-methylformamide.

The invention has the beneficial effects that:

1. according to the preparation method, adenine is used as a main ligand, citric acid is used as a second ligand to prepare the MOF structure, and compared with adenine used as a single ligand, the structural adjustability of the material can be realized, and the porosity is improved.

2. Selected central ion (Zn) of the invention²⁺) The sodium citrate is used as anticoagulant, phlegm eliminating medicine and diuretic in medicine industry, and the metal organic frame material comprising the human body friendly matter has high biocompatibility.

3. The metal organic framework material synthesized by the invention can become a sustained and controlled release drug carrier material with good biocompatibility.

Description of the drawings:

FIG. 1 is an XRD spectrum of the powder prepared in example 2 of the present invention.

FIG. 2 is an SEM spectrum of the powder prepared in example 2 of the present invention.

FIG. 3 is an XRD spectrum of the powder prepared in example 8 of the present invention.

FIG. 4 is an SEM spectrum of a powder prepared in example 8 of the present invention.

The specific implementation mode is as follows:

the invention will be further illustrated with reference to the following specific examples. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. Further, it should be understood that various changes or modifications of the present invention may be made by those skilled in the art after reading the teaching of the present invention, and such equivalents may fall within the scope of the invention defined by the appended claims.

The specific implementation mode is as follows:

example 1

Dissolving 0.0015mol of adenine (0.2027g) in 30mLN, N-2 methylformamide, heating to 140 ℃ while magnetically stirring until the adenine is completely dissolved in the N, N-2 methylformamide, and cooling to room temperature to obtain a solution A with the concentration of 0.05 mol/L; 0.005mol trisodium citrate (1.2905g) was dissolved in 10mLH₂In O, magnetically stirring for 5min until trisodium citrateCompletely dissolve in H₂In O, obtaining a solution B with the concentration of 0.5 mol/L; dissolving 0.005mol of zinc acetate (1.0975g) in 20mLN, N-2 methyl formamide, and carrying out magnetic stirring for 5min until the zinc acetate is completely dissolved in the N, N-2 methyl formamide to obtain a solution C with the concentration of 0.25 mol/L; firstly, measuring 4.5mL of solution B and 30mL of solution A by using a pipette, and mixing to obtain a solution D; adding 12mL of ethanol and 3mL of water into the solution D in sequence to obtain a solution E; taking a pipette to measure 12mL of solution C and solution E, mixing, stirring for 15s by using a glass rod to obtain a reaction solution, and then transferring the reaction solution to a polytetrafluoroethylene lining reaction kettle; putting the polytetrafluoroethylene lining reaction kettle into an oven, heating to 120 ℃, and then heating at 120 ℃ for 30 h; after heating is finished, after the reaction liquid is cooled to room temperature, opening the lining reaction kettle, pouring out supernatant, adding an organic solvent N, N-2 methylformamide into the residual white precipitate, performing suction filtration treatment for 3 times, washing for 3 times by using absolute ethyl alcohol, after centrifugation is finished, placing the obtained product in a drying oven, drying for 7 hours at 100 ℃, and after subsequent treatment is finished, obtaining material powder.

Example 2

Dissolving 0.0015mol of adenine (0.2027g) in 30mLN, N-2 methylformamide, heating to 140 ℃ while magnetically stirring until the adenine is completely dissolved in the N, N-2 methylformamide, and cooling to room temperature to obtain a solution A with the concentration of 0.05 mol/L; 0.005mol trisodium citrate (1.2905g) was dissolved in 10mLH₂Magnetically stirring for 5min in O until trisodium citrate is completely dissolved in H₂In O, obtaining a solution B with the concentration of 0.5 mol/L; dissolving 0.005mol of zinc acetate (1.0975g) in 20mLN, N-2 methyl formamide, and carrying out magnetic stirring for 5min until the zinc acetate is completely dissolved in the N, N-2 methyl formamide to obtain a solution C with the concentration of 0.25 mol/L; firstly, measuring 6mL of solution B and 30mL of solution A by using a pipette, and mixing to obtain a solution D; adding 12mL of ethanol and 3mL of water into the solution D in sequence to obtain a solution E; taking a pipette to measure 12mL of solution C and solution E, mixing, stirring for 15s by using a glass rod to obtain a reaction solution, and then transferring the reaction solution to a polytetrafluoroethylene lining reaction kettle; putting the polytetrafluoroethylene lining reaction kettle into an oven, heating to 110 ℃, and then heating for 36h at 110 ℃; after the end of the heating, the heating is carried out,after the reaction liquid is cooled to room temperature, opening the lining reaction kettle, pouring out supernatant, adding an organic solvent N, N-2 methyl formamide into the residual white precipitate, carrying out suction filtration treatment for 3 times, washing for 3 times with absolute ethyl alcohol, after centrifugation is finished, placing the obtained product in a drying oven, drying for 7 hours at 100 ℃, and obtaining material powder after subsequent treatment is finished.

Example 3

Dissolving 0.0015mol of adenine (0.2027g) in 30mLN, N-2 methylformamide, heating to 140 ℃ while magnetically stirring until the adenine is completely dissolved in the N, N-2 methylformamide, and cooling to room temperature to obtain a solution A with the concentration of 0.05 mol/L; 0.005mol trisodium citrate (1.2905g) was dissolved in 10mLH₂Magnetically stirring for 5min in O until trisodium citrate is completely dissolved in H₂In O, obtaining a solution B with the concentration of 0.5 mol/L; dissolving 0.005mol of zinc acetate (1.0975g) in 20mLN, N-2 methyl formamide, and carrying out magnetic stirring for 5min until the zinc acetate is completely dissolved in the N, N-2 methyl formamide to obtain a solution C with the concentration of 0.25 mol/L; firstly, measuring 6mL of solution B and 30mL of solution A by using a pipette, and mixing to obtain a solution D; adding 12mL of ethanol and 3mL of water into the solution D in sequence to obtain a solution E; taking a pipette to measure 18mL of solution C and solution E, mixing, stirring for 15s by using a glass rod to obtain a reaction solution, and then transferring the reaction solution to a polytetrafluoroethylene lining reaction kettle; putting the polytetrafluoroethylene lining reaction kettle into an oven, heating to 130 ℃, and then heating at 130 ℃ for 24 hours; after heating is finished, after the reaction liquid is cooled to room temperature, opening the lining reaction kettle, pouring out supernatant, adding an organic solvent N, N-2 methylformamide into the residual white precipitate, performing suction filtration treatment for 3 times, washing for 3 times by using absolute ethyl alcohol, after centrifugation is finished, placing the obtained product in a drying oven, drying for 5 hours at 110 ℃, and after subsequent treatment is finished, obtaining material powder.

Example 4

Dissolving 0.0015mol of adenine (0.2027g) in 30mLN, N-2 methylformamide, heating to 130 ℃ while magnetically stirring until the adenine is completely dissolved in the N, N-2 methylformamide, and cooling to room temperature to obtain a solution A with the concentration of 0.05 mol/L; adding 0.005mol of lemonTrisodium citrate (1.2905g) dissolved in 10mLH₂Magnetically stirring for 5min in O until trisodium citrate is completely dissolved in H₂In O, obtaining a solution B with the concentration of 0.5 mol/L; dissolving 0.005mol of zinc acetate (1.0975g) in 20mLN, N-2 methyl formamide, and carrying out magnetic stirring for 5min until the zinc acetate is completely dissolved in the N, N-2 methyl formamide to obtain a solution C with the concentration of 0.25 mol/L; firstly, measuring 6mL of solution B and 30mL of solution A by using a pipette, and mixing to obtain a solution D; adding 12mL of ethanol and 3mL of water into the solution D in sequence to obtain a solution E; taking a pipette to measure 18mL of solution C and solution E, mixing, uniformly stirring to obtain a reaction solution, and transferring the reaction solution to a polytetrafluoroethylene lining reaction kettle; putting the polytetrafluoroethylene lining reaction kettle into an oven, heating to 110 ℃, and then heating for 36h at 110 ℃; after heating is finished, after the reaction liquid is cooled to room temperature, opening the lining reaction kettle to pour out supernatant, adding an organic solvent N, N-2 methyl formamide into the residual white precipitate, performing suction filtration treatment for 3 times, washing for 3 times by using absolute ethyl alcohol, after centrifugation is finished, placing the obtained product in a drying box, drying for 6 hours at 110 ℃, and after subsequent treatment is finished, obtaining material powder.

Example 5

Dissolving 0.0007mol of adenine (0.0946g) in 10mLN, N-2 methylformamide, heating to 130 ℃ while magnetically stirring until the adenine is completely dissolved in the N, N-2 methylformamide, and cooling to room temperature to obtain a solution A with the concentration of 0.07 mol/L; 0.005mol trisodium citrate (1.2905g) was dissolved in 10mLH₂Magnetically stirring for 5min in O until trisodium citrate is completely dissolved in H₂In O, obtaining a solution B with the concentration of 0.5 mol/L; dissolving 0.002mol of zinc acetate (0.4390g) in 40mLN, N-2 methyl formamide, and magnetically stirring for 5min until the zinc acetate is completely dissolved in the N, N-2 methyl formamide to obtain a solution C with the concentration of 0.05 mol/L; firstly, measuring 2.8mL of solution B and 10mL of solution A by using a pipette, and mixing to obtain a solution D; adding 6mL of ethanol and 1.5mL of water into the solution D in sequence to obtain a solution E; mixing 35mL of the solution C with the solution E, stirring for 15s by using a glass rod to obtain a reaction solution, and then transferring the reaction solution to a polytetrafluoroethylene lining reaction kettle; putting a polytetrafluoroethylene lining reaction kettle intoHeating to 110 ℃ in an oven, and then heating for 36h at 110 ℃; after heating is finished, after the reaction liquid is cooled to room temperature, opening the lining reaction kettle to pour out supernatant, adding an organic solvent N, N-2 methyl formamide into the residual white precipitate, performing suction filtration treatment for 3 times, washing for 3 times by using absolute ethyl alcohol, after centrifugation is finished, placing the obtained product in a drying box, drying at 120 ℃ for 7 hours, and after subsequent treatment is finished, obtaining material powder.

Example 6

Dissolving 0.0018mol of adenine (0.2432g) in 30mLN, N-2-methylformamide, heating to 130 ℃ while magnetically stirring until the adenine is completely dissolved in the N, N-2-methylformamide, and cooling to room temperature to obtain a solution A with the concentration of 0.06 mol/L; 0.005mol trisodium citrate (1.2905g) was dissolved in 10mLH₂Magnetically stirring for 5min in O until trisodium citrate is completely dissolved in H₂In O, obtaining a solution B with the concentration of 0.5 mol/L; dissolving 0.003mol of zinc acetate (0.6585g) in 20mLN, N-2 methyl formamide, and carrying out magnetic stirring for 5min until the zinc acetate is completely dissolved in the N, N-2 methyl formamide to obtain a solution C with the concentration of 0.15 mol/L; firstly, measuring 6mL of solution B and 25mL of solution A by using a pipette, and mixing to obtain a solution D; adding 10mL of ethanol and 2.5mL of water into the solution D in sequence to obtain a solution E; taking a pipette to measure 20mL of the solution C and the solution E, mixing, stirring for 15s by using a glass rod to obtain a reaction solution, and then transferring the reaction solution to a polytetrafluoroethylene lining reaction kettle; putting the polytetrafluoroethylene lining reaction kettle into an oven, heating to 120 ℃, and then heating at 120 ℃ for 30 h; after heating is finished, after the reaction liquid is cooled to room temperature, opening the lining reaction kettle to pour out supernatant, adding an organic solvent N, N-2 methyl formamide into the residual white precipitate, performing suction filtration treatment for 3 times, washing for 3 times by using absolute ethyl alcohol, after centrifugation is finished, placing the obtained product in a drying box, drying for 6 hours at 130 ℃, and after subsequent treatment is finished, obtaining material powder.

Example 7

Dissolving 0.0015mol adenine (0.2027g) in 30ml of N, N-2-methylformamide, and heating to 130 ℃ while magnetically stirring until the adenine is completely dissolved in the N, N-2-methylformamideCooling to room temperature in amine to obtain a solution A with the concentration of 0.05 mol/L; 0.003mol trisodium citrate (0.7743g) was dissolved in 10mLH₂Magnetically stirring for 5min in O until trisodium citrate is completely dissolved in H₂In O, obtaining a solution B with the concentration of 0.3 mol/L; dissolving 0.004mol of zinc acetate (0.8780g) in 20mLN, N-2 methyl formamide, and carrying out magnetic stirring for 5min until the zinc acetate is completely dissolved in the N, N-2 methyl formamide to obtain a solution C with the concentration of 0.2 mol/L; firstly, measuring 7.5mL of solution B and 30mL of solution A by using a pipette, and mixing to obtain a solution D; adding 12mL of ethanol and 3mL of water into the solution D in sequence to obtain a solution E; taking a pipette to measure 18.75mL of solution C and solution E, mixing, stirring for 15s by using a glass rod to obtain a reaction solution, and then transferring the reaction solution to a polytetrafluoroethylene lining reaction kettle; putting the polytetrafluoroethylene lining reaction kettle into an oven, heating to 130 ℃, and then heating at 130 ℃ for 24 hours; after heating is finished, after the reaction liquid is cooled to room temperature, opening the lining reaction kettle to pour out supernatant, adding an organic solvent N, N-2 methylformamide into the residual white precipitate, performing suction filtration treatment for 3 times, washing for 3 times by using absolute ethyl alcohol, after centrifugation is finished, placing the obtained product in a drying oven, drying for 6 hours at 150 ℃, and after subsequent treatment is finished, obtaining material powder.

Example 8

Dissolving 0.001mol of adenine (0.1351g) in 20mLN, N-2 methylformamide, heating to 130 ℃ while magnetically stirring until the adenine is completely dissolved in the N, N-2 methylformamide, and cooling to room temperature to obtain a solution A with the concentration of 0.05 mol/L; 0.002mol trisodium citrate (0.5162g) was dissolved in 10mLH₂Magnetically stirring for 5min in O until trisodium citrate is completely dissolved in H₂In O, obtaining a solution B with the concentration of 0.2 mol/L; dissolving 0.003mol of zinc acetate (0.6585g) in 30mLN, N-2 methyl formamide, and carrying out magnetic stirring for 5min until the zinc acetate is completely dissolved in the N, N-2 methyl formamide to obtain a solution C with the concentration of 0.1 mol/L; firstly, 10mL of solution B and solution A are mixed to obtain solution D; adding 8mL of ethanol and 2mL of water into the solution D in sequence to obtain a solution E; then 30mL of the solution C and the solution E were mixed and stirred with a glass rod for 15 seconds to obtain a reaction solution, which was then transferred to PolytetrafluoroethyleneIn an ethylene lined reaction kettle; putting the polytetrafluoroethylene lining reaction kettle into an oven, heating to 110 ℃, and then heating for 36h at 110 ℃; after heating is finished, after the reaction liquid is cooled to room temperature, opening the lining reaction kettle to pour out supernatant, adding an organic solvent N, N-2 methyl formamide into the residual white precipitate, performing suction filtration treatment for 3 times, washing for 3 times by using absolute ethyl alcohol, after centrifugation is finished, placing the obtained product in a drying oven, drying for 5 hours at 170 ℃, and after subsequent treatment is finished, obtaining material powder.