A covalent organic framework material and a preparation method and application thereof

Abstract

The application provides a kind of covalent organic framework material and its preparation method and application, the preparation method comprises the following steps: (1) the compound containing metal ion is pre-coordinated with organic ligand tetraamino phenyl porphyrin to form metalized monomer;(2) the metalized monomer obtained in step (1) is reacted with 1,3,5-triformylbenzene to obtain the covalent organic framework material.The application designs metal-containing organic monomer, directly builds metal coordination site in the synthesis process of COF, realizes metal-organic skeleton integration, thereby avoids the problem that metal active site is easy to lose, effectively improves the antibacterial durability of metal covalent organic framework material.

Description

TECHNICAL FIELD

[0001] The present application belongs to the field of functional materials and coordination chemistry, and particularly relates to a covalent organic framework material and a preparation method and application thereof, in particular to a covalent organic framework material containing silver, zinc or copper and a preparation method and application thereof. BACKGROUND

[0002] Metal ions (such as silver, zinc, copper) can destroy the bacterial cell membrane by positive and negative charge adsorption, penetrate and combine with sulfhydryl (-SH) to inactivate enzymes, and interfere with DNA replication, thereby achieving the purpose of inhibiting bacteria. Currently, there are antibacterial agents on the market that load silver, zinc and copper on zeolite, silica gel and other carriers through physical adsorption, ion exchange and other methods.

[0003] Covalent organic frameworks (COFs) have attracted much attention in the fields of catalysis, sensing and biomedicine in recent years due to their high specific surface area, tunable pore structure and chemical modification. In the prior art, there are studies on imparting antibacterial properties to COFs by loading metals (such as silver, zinc, copper). For example, CN 117624626 A discloses a COF material and a preparation method for efficiently killing bacteria, but this method relies on the synthesis of COFs and then the modification of silver loading, which may destroy the pore structure of COFs, and there is a problem of easy loss of metal active sites, resulting in low durability of the antibacterial agent.

[0004] Therefore, it is a research focus in the field to develop a covalent organic framework material with durable antibacterial effect that can solve the problem of easy loss of metal active sites. SUMMARY

[0005] In view of the deficiencies of the prior art, the purpose of the present application is to provide a covalent organic framework material and a preparation method and application thereof, in particular to provide a covalent organic framework material containing silver, zinc or copper and a preparation method and application thereof. The present application directly constructs metal coordination sites in the synthesis process of COFs by designing metal-containing organic monomers, realizes the integration of metal-organic framework, and thus avoids the problem of easy loss of metal active sites, effectively improving the antibacterial durability of the metal covalent organic framework material.

[0006] To achieve this purpose, the present application adopts the following technical solutions:

[0007] On the one hand, the present application provides a preparation method of a covalent organic framework material, which comprises the following steps:

[0008] (1) pre-coordinate a compound containing metal ions and an organic ligand tetraaminophenyl porphyrin to form a metalized monomer, and the reaction formula is as follows:

[0009] ;

[0010] (2) reacting the metallated monomer obtained in step (1) with 1,3,5-triformylbenzene to obtain the covalent organic framework material, the reaction formula is as follows:

[0011]

[0012] wherein M represents a metal ion, and the wavy line represents a further extension of the repeat unit structure.

[0013] In the present application, by pre-coordinating the compound containing metal ions with the organic ligand tetraaminophenyl porphyrin to form a metallated monomer, and then reacting with 1,3,5-triformylbenzene to form a covalent organic framework material, the metal-organic framework is integrated, thereby avoiding the problem of easy loss of metal active sites, and effectively improving the antibacterial durability of silver, zinc, and copper-containing covalent organic framework materials.

[0014] Preferably, the metal ion in the compound containing metal ions in step (1) is selected from zinc ion, silver ion or copper ion.

[0015] Preferably, the compound containing metal ions is zinc acetate, silver nitrate or copper sulfate.

[0016] Preferably, the molar ratio of tetraaminophenyl porphyrin to the compound containing metal ions in step (1) is 1:1.1 to 1:1.5, for example 1:1.1, 1:1.2, 1:1.3, 1:1.4 or 1:1.5. In the present application, the excess of metal salt ensures complete metallization of the porphyrin.

[0017] Preferably, the pre-coordination in step (1) is carried out under nitrogen protection.

[0018] Preferably, the pre-coordination in step (1) is carried out under constant temperature stirring at 60-80°C (for example 60°C, 65°C, 70°C, 75°C or 80°C) for 12-24 h, for example 12 h, 15 h, 18 h, 20 h, 22 h or 24 h.

[0019] Preferably, the pre-coordination in step (1) is carried out in a solvent selected from polar organic solvents, preferably DMF (N,N-dimethylformamide) or DMSO (dimethyl sulfoxide). The strong polarity of the solvent in the present application can promote the coordination of amino groups with metal ions.

[0020] Preferably, the molar ratio of the metallated monomer to 1,3,5-triformylbenzene (TFB) in step (2) is 1:1.2 to 1:1.5, for example 1:1.2, 1:1.25, 1:1.3, 1:1.35, 1:1.4, 1:1.45 or 1:1.5, in the present application, the excess of TFB to improve the crosslinking degree.

[0021] Preferably, the reaction in step (2) is carried out in a solvent selected from dichloromethane and / or dichloroethane.

[0022] Preferably, the mass ratio of the solvent to 1,3,5-triformylbenzene in step (2) is 10:1 to 50:1, such as 10:1, 13:1, 15:1, 18:1, 20:1, 25:1, 28:1, 30:1, 35:1, 38:1, 40:1, 45:1, 48:1 or 50:1; the amount of the solvent is used to ensure that all reactants are dissolved.

[0023] Preferably, the reaction in step (2) is carried out in the presence of a catalyst.

[0024] Preferably, the catalyst is selected from acetic acid.

[0025] Preferably, the molar ratio of the catalyst to 1,3,5-triformylbenzene is 0.001:1 to 0.01:1, such as 0.001:1, 0.005:1, 0.008:1, 0.01:1, etc.

[0026] Preferably, the temperature of the reaction in step (2) is 120-130℃ (such as 120℃, 125℃, 128℃ or 130℃), and the reaction time is 48-72 h, such as 48 h, 50 h, 53 h, 55 h, 58 h, 60 h, 62 h, 64 h, 68 h or 72 h.

[0027] In another aspect, the present application provides a covalent organic framework material prepared by the preparation method as described above.

[0028] In another aspect, the present application provides an antibacterial material comprising the covalent organic framework material as described above.

[0029] In another aspect, the present application provides use of the covalent organic framework material or the antibacterial material as described above in the preparation of a catalytic material, a biosensing material or a biomedical material.

[0030] Compared with the prior art, the present application has the following beneficial effects:

[0031] The present application realizes the integration of metal-organic framework by forming a metalized monomer by pre-ligating a compound containing metal ions with an organic ligand tetraamino phenyl porphyrin, and then reacting with 1,3,5-triformylbenzene to form a covalent organic framework material, thereby avoiding the problem of easy loss of metal active sites, effectively improving the antibacterial durability of the metal covalent organic framework material, and having a wide application prospect. DETAILED DESCRIPTION

[0032] The technical solutions of the present application are further illustrated below through specific embodiments. Those skilled in the art should understand that the embodiments are only used to help understand the present application and should not be regarded as specific limitations on the present application.

[0033] Embodiment 1

[0034] The present embodiment provides a covalent organic framework material, and a preparation method thereof includes the following steps:

[0035] (1) DMF is used as the reaction solvent, and the molar ratio of TAPP (tetraaminophenyl porphyrin) to zinc acetate is 1:1.2. Under the protection of nitrogen, the reaction is stirred at 60°C for 24h. After the reaction is completed, the reaction solution is cooled, 5 times deionized water is added to precipitate the product, the solid is collected by centrifugation, washed with deionized water for 3 times, and vacuum dried (50°C, 6h) to obtain Zn-TAPP. The reaction formula is as follows:

[0036]

[0037] (2) Dichloromethane is used as the reaction solvent (mass ratio of dichloromethane to TFB is 25:1), and the molar ratio of Zn-TAPP to TFB is 1:1.2. Acetic acid (molar ratio of acetic acid to TFB is 0.001:1) is used as the catalyst, and the reaction is carried out at 120°C for 48h. After the reaction is completed, the reaction solution is washed with tetrahydrofuran for 1 time, washed with methanol for 2 times, and vacuum dried (50°C, 6h) to obtain zinc-loaded COFs powder. The reaction formula is as follows:

[0038] .

[0039] Embodiment 2

[0040] The present embodiment provides a covalent organic framework material, and a preparation method thereof includes the following steps:

[0041] (1) DMSO is used as the reaction solvent, and the molar ratio of TAPP to silver nitrate is 1:1.1. Under the protection of nitrogen, the reaction is stirred at 80°C for 12h. After the reaction is completed, the reaction solution is cooled, 3 times deionized water is added to precipitate the product, the solid is collected by centrifugation, washed with deionized water for 3 times, and vacuum dried (50°C, 6h) to obtain Ag-TAPP.

[0042] (2) The reaction was carried out using dichloroethane as the reaction solvent (mass ratio of dichloroethane to TFB was 50:1), the molar ratio of Ag-TAPP to TFB was 1:1.5, acetic acid (molar ratio of acetic acid to TFB was 0.005:1) was used as the catalyst, and the reaction was carried out at 120°C for 72 hours. After the reaction was completed, the product was washed with tetrahydrofuran once and methanol twice, and then vacuum dried (50°C, 6 hours) to obtain the silver-loaded COFs powder.

[0043] Example 3

[0044] The present example provides a kind of covalent organic framework material, and its preparation method includes the following steps:

[0045] (1) The reaction was carried out using DMSO as the reaction solvent, and the molar ratio of TAPP to copper sulfate was 1:1.2. The reaction was carried out under nitrogen protection at 70°C for 18 hours. After the reaction was completed, the product was precipitated by adding 1 times deionized water to the reaction solution, and then the solid was collected by centrifugation, washed with deionized water three times, and vacuum dried (50°C, 6 hours) to obtain Cu-TAPP.

[0046] (2) The reaction was carried out using dichloromethane as the reaction solvent (mass ratio of dichloromethane to TFB was 10:1), the molar ratio of Cu-TAPP to TFB was 1:1.3, acetic acid (molar ratio of acetic acid to TFB was 0.01:1) was used as the catalyst, and the reaction was carried out at 120°C for 72 hours. After the reaction was completed, the product was washed with tetrahydrofuran once and methanol twice, and then vacuum dried (50°C, 6 hours) to obtain the copper-loaded COFs powder.

[0047] Comparative Example 1

[0048] First, 25.2g of silver nitrate was dissolved in 1000g of deionized water at room temperature, so that the silver nitrate was fully dissolved. 100g of COFs (purchased from Yaoke New Materials (Suzhou) Co., Ltd., NKCOF-45) was slowly added to the above solution, and the structure of the COFs is as follows:

[0049] .

[0050] The solution was heated to 80°C and reacted for 24 hours. The reaction was ensured to be complete by testing the silver content in the supernatant after centrifugation (supernatant silver content <100ppm). After the reaction was completed, the silver-loaded COFs was centrifuged, washed with deionized water three times, and vacuum dried (50°C, 6 hours) to obtain the silver-loaded COFs powder.

[0051] Comparative Example 2

[0052] The present example provides a kind of covalent organic framework material, and its preparation method includes the following steps:

[0053] (1) The reaction was carried out with dichloroethane as the reaction solvent (mass ratio of TFB: 50:1), TAPP and TFB in a molar ratio of 1:1.5, acetic acid (molar ratio of TFB: 0.005:1) as the catalyst, and reaction at 120°C for 72h. After the reaction, the product was washed with tetrahydrofuran once, washed with methanol twice, and vacuum dried (50°C, 6h) to obtain COFs powder.

[0054] (2) First, 25.2g of silver nitrate was weighed into 1000g of deionized water at room temperature to make the silver nitrate fully dissolved. 100g of COFs powder from step (1) was slowly added and heated to 80°C for 12 hours to ensure the reaction was complete (supernatant silver content <100ppm). After the reaction, the silver-loaded COFs was centrifuged, washed with deionized water 3 times, and vacuum dried (50°C, 6h) to obtain silver-loaded COFs powder.

[0055] The covalent organic framework materials (or COFs powder) obtained from Examples 1-3 and Comparative Examples 1-2 were blended with PP chips by powder mixing, and the plastic particles containing COFs were injection molded into samples by an injection molding machine. The process steps and conditions were the same between the examples and comparative examples except for the different covalent organic framework materials.

[0056] Antibacterial test standard: JC / T 939-2004 (Appendix A);

[0057] Evaluation criteria: Class I antibacterial rate ≥ 99%, Class II antibacterial rate ≥ 90%;

[0058] Test content:

[0059] ① The bacteria were quantitatively inoculated on the sample to be tested, and the bacteria were uniformly contacted with the sample by the method of sticking film. After a certain time (72 hours for E. coli and 96 hours for S. aureus), the number of viable bacteria in the sample was measured, and the antibacterial rate of the sample was calculated.

[0060] ② Polyethylene film: the standard size is (40±2) mm x (40±2) mm, and the thickness is (0.05~0.10) mm. The bacteria concentration on the sample film is kept constant. Soak in 70% ethanol solution for 1 min, then rinse with sterile water and dry naturally.

[0061] ③ Inoculation and culture of bacteria: spread the bacteria solution on the sample with an area of 16 cm, and drop 0.2ml of test bacteria solution on the sample. Make sure the bacteria are evenly contacted with the sample and place it in a sterile plate at (37±1)℃, relative humidity RH>90% for 24h.

[0062] (4) Elution: Take the sample cultured for 24 h, add 20 ml of washing solution, repeatedly wash the sample, and then count the viable bacteria after culturing at (37±1) °C for (24-48) h. The viable bacteria in the washing solution are determined according to the method of GB 4789.2.

[0063] (5) Test and calculate the number of colonies.

[0064] Test standard of antibacterial durability: JC / T 939-2004;

[0065] Evaluation standard: the bacterial durability is ≥ 90%.

[0066] Test content:

[0067] Soaking: The sample soaked in a distilled water bath at a temperature of (50±2) °C for 16 h is subjected to the antibacterial performance test according to the above antibacterial test procedure.

[0068] The test results are shown in Table 1.

[0069] Table 1

[0070]

[0071] The applicant declares that the covalent organic framework material, the preparation method and the application thereof of the present application are illustrated by the above examples, but the present application is not limited to the above examples, that is, it does not mean that the present application must rely on the above examples to be implemented. It should be understood by those skilled in the art that any improvement of the present application, equivalent replacement of each raw material of the product of the present application, addition of auxiliary ingredients, selection of specific modes, etc. fall within the protection scope and disclosure scope of the present application.

Claims

1. A method of preparing a covalent organic framework material, characterized in that, The preparation method comprises the following steps: (1) a compound containing metal ions is pre-coordinated with an organic ligand tetraamino phenyl porphyrin to form a metalated monomer, and the reaction formula is as follows: ； (2) the metalated monomer obtained in step (1) is reacted with 1,3,5-triformylbenzene to obtain the covalent organic framework material, and the reaction formula is as follows: ； wherein M represents a metal ion, and the wavy line represents a further extension of the repeating unit structure; In step (2), the molar ratio of the metalated monomer to 1,3,5-triformylbenzene is 1:1.2-1:1.5; In step (2), the reaction temperature is 120-130 DEG C, and the reaction time is 48-72 h.

2. The production method according to claim 1, characterized by, In step (1), the metal ion in the compound containing metal ions is selected from zinc ion, silver ion or copper ion.

3. The preparation method according to claim 1, characterized in that The compound containing metal ions is zinc acetate, silver nitrate or copper sulfate; In step (1), the molar ratio of tetraamino phenyl porphyrin to the compound containing metal ions is 1:1.1-1:1.

5.

4. The method of claim 1, wherein, In step (1), the pre-coordination is carried out under nitrogen protection. In step (1), the pre-coordination is carried out under constant temperature stirring at 60-80 DEG C for 12-24 h.

5. The preparation method according to claim 1, characterized in that In step (1), the pre-coordination is carried out in a solvent selected from polar organic solvents N, N-dimethylformamide or dimethyl sulfoxide.

6. The method of claim 1, wherein, In step (2), the reaction is carried out in a solvent selected from dichloromethane and / or dichloroethane; In step (2), the mass ratio of the solvent to 1,3,5-triformylbenzene is 10:1-50:

1.

7. The production method according to any one of claims 1 to 6, characterized by, In step (2), the reaction is carried out in the presence of a catalyst; The catalyst is selected from any one or a combination of at least two of acetic acid, propionic acid or boron trifluoride etherate; The molar ratio of the catalyst to 1,3,5-triformylbenzene is 0.001:1-0.01:

1.

8. The covalent organic framework material prepared by the preparation method according to any one of claims 1-7.

9. An antibacterial material, characterized by, The antibacterial material comprises the covalent organic framework material according to claim 8.

10. Application of the covalent organic framework material according to claim 8 or the antibacterial material according to claim 9 in the preparation of catalytic materials, biosensing materials or biomedical materials.

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