One-dimensional covalent organic framework material

Abstract

The invention belongs to the field of covalent organic framework materials, and discloses a one-dimensional covalent organic framework material. The one-dimensional covalent organic framework material is prepared by carrying out a Schiff base reaction on highly symmetrical 3, 6-di (4-formylbenzene) carbazole with an included angle of 90 degrees and highly symmetrical 5, 10, 15, 20-tetra (4-aminophenyl) porphyrin with an included angle of 90 degrees in the presence of a solvent and a catalyst to generate imine bonds. The nanoscale one-dimensional covalent organic framework material (namely a one-dimensional covalent organic framework material machinable solution) is obtained by inhibiting the speed of generating imine bonds through a Schiff base reaction.

Description

Technical Field

[0001] The invention belongs to the field of covalent organic framework materials, and more specifically, relates to a one-dimensional covalent organic framework material. Background Art

[0002] Covalent organic framework materials are a class of porous crystalline materials composed of organic molecular units connected by strong covalent bonds. This type of material has the advantages of highly ordered structure, large specific surface area, adjustable pore size and chemical stability, and shows broad application prospects in gas storage and separation, catalysis, optoelectronic materials, sensing and drug delivery. Unlike two-dimensional and three-dimensional covalent organic frameworks, one-dimensional covalent organic frameworks are formed by covalently connecting building blocks in only one dimension. These structures will further aggregate with each other driven by weak van der Waals forces and π-π stacking. The linear structure and weak non-covalent interactions of one-dimensional covalent organic framework materials allow more active sites to be exposed, which is particularly beneficial for catalytic materials because more active sites mean higher catalytic efficiency.

[0003] However, the one-dimensional covalent organic framework materials usually prepared are micron-sized bulk materials, and it is difficult to make stable processable solutions even through ultrasonic dispersion and other means. However, these stable processable solutions can improve the performance and stability of electrode materials in energy storage and conversion, such as lithium-ion batteries and supercapacitors. In the field of catalysis, covalent organic framework material solutions can be used to prepare efficient catalyst carriers to improve catalytic efficiency and selectivity. In terms of gas separation and storage, materials prepared by solution can achieve efficient gas adsorption and separation. In addition, covalent organic framework material solutions are also widely used in optoelectronic materials, such as solar cells and photodetectors, which can improve photoelectric conversion efficiency. In the biomedical field, covalent organic framework material solutions can be used to prepare drug delivery systems and bioimaging materials to achieve targeted therapy and high-sensitivity detection. In other words, once the covalent organic framework material is prepared into a processable solution, it can be convenient to prepare thin films, coatings, nanoparticles and composite materials. In short, one-dimensional covalent organic framework material processable solutions provide new possibilities for materials science and engineering technology and have broad application prospects.

[0004] Therefore, it is urgent to propose a new one-dimensional covalent organic framework material. Summary of the invention

[0005] The purpose of the present invention is to provide a one-dimensional covalent organic framework material in view of the deficiencies of the prior art. The present invention obtains a nanoscale one-dimensional covalent organic framework material (i.e., a one-dimensional covalent organic framework material processable solution) by suppressing the speed of generating imine bonds by Schiff base reaction.

[0006] In order to achieve the above-mentioned object, the present invention provides a one-dimensional covalent organic framework material, wherein the one-dimensional covalent organic framework material is obtained by generating imine bonds through Schiff base reaction of highly symmetrical 3,6-di(4-formaldehydephenyl)carbazole with a 90° angle and highly symmetrical 5,10,15,20-tetrakis(4-aminophenyl)porphyrin with a 90° angle under solvent and catalyst conditions.

[0007] In the present invention, the structural formula of 3,6-di(4-formaldehydephenyl)carbazole which is highly symmetrical and has a 90° angle is shown below:

[0008]

[0009] In the present invention, the structural formula of 5,10,15,20-tetrakis(4-aminophenyl)porphyrin, which is highly symmetrical and has an angle of 90°, is as follows:

[0010]

[0011] According to the present invention, preferably, the structural formula of the one-dimensional covalent organic framework material is as follows:

[0012]

[0013] According to the present invention, preferably, the one-dimensional covalent organic framework material has a size of nanometer scale.

[0014] According to the present invention, preferably, the method for preparing a nanoscale one-dimensional covalent organic framework material comprises the following steps:

[0015] S1: mixing and stirring the highly symmetrical 3,6-di(4-formaldehydephenyl)carbazole and the first solvent having an angle of 90° to obtain a mixed solution a;

[0016] S2: Mix and stir the highly symmetrical 5,10,15,20-tetrakis(4-aminophenyl)porphyrin with an angle of 90°, the second solvent and the first catalyst to obtain a mixed solution b;

[0017] S3: The mixed solution a and the mixed solution b are mixed and stirred uniformly and subjected to a Schiff base reaction to obtain a solution c; the solution c is mixed uniformly with ethanol and subjected to an aging treatment to obtain the nanoscale one-dimensional covalent organic framework material.

[0018] According to the present invention, preferably, the molar ratio of highly symmetrical 3,6-di(4-formaldehydephenyl)carbazole with a 90° angle, highly symmetrical 5,10,15,20-tetrakis(4-aminophenyl)porphyrin with a 90° angle and the first catalyst is (1.5-2.5):1:(1.5-2.5).

[0019] According to the present invention, preferably, the first solvent and the second solvent are each independently at least one of 1,2-dichlorobenzene, 1-butanol, 1,3,5-trimethylbenzene, 1,4-dioxane, N,N-dimethylacetamide, ethanol and water.

[0020] According to the present invention, preferably, the first catalyst is at least one of diglycolic acid, acetic acid and glutaric acid.

[0021] The method for suppressing the speed of generating imine bonds by Schiff base reaction is as follows: 5,10,15,20-tetrakis(4-aminophenyl)porphyrin and diglycolic acid are mixed and dissolved, and the amino group and the carboxyl group thereof form a hydrogen bond, and when 3,6-di(4-aldehydephenyl)carbazole is mixed, the hydrogen bond hinders the interaction between the aldehyde group and the amino group, thereby suppressing the speed of generating imine bonds; adding a proper amount of water to the mixed solution b, increasing the water content in the reaction system (water is the product of Schiff base reaction), and also suppressing the speed of generating imine bonds; and at the same time, a lower reaction temperature can also suppress the speed of generating imine bonds.

[0022] According to the present invention, preferably, in step S1, the mixing and stirring temperature is 80-100° C. and the time is 5-20 min.

[0023] According to the present invention, preferably, in step S2, the mixing and stirring temperature is 80-100° C. and the time is 5-20 min.

[0024] According to the present invention, preferably, in step S3:

[0025] The temperature of the Schiff base reaction is 80-100°C and the time is 5-20 minutes;

[0026] The volume ratio of the solution c to ethanol is (10-200): (1000-5000);

[0027] The aging treatment time is 20-40h.

[0028] According to the present invention, preferably, the size of the one-dimensional covalent organic framework material is micrometer-sized, and micrometer-sized one-dimensional covalent organic framework materials cannot become stable processable solutions.

[0029] According to the present invention, preferably, the method for preparing a micron-sized one-dimensional covalent organic framework material comprises the following steps:

[0030] (1) ultrasonically mixing highly symmetrical 3,6-di(4-formaldehydephenyl)carbazole having an angle of 90°, highly symmetrical 5,10,15,20-tetrakis(4-aminophenyl)porphyrin having an angle of 90°, a third solvent, and a second catalyst to obtain a uniform mixed solution;

[0031] (2) degassing and sealing the equipment containing the mixed uniform solution of step (1) with liquid nitrogen;

[0032] (3) subjecting the mixed uniform solution in the device treated in step (2) to a Schiff base reaction to obtain a precipitate, which is then filtered, washed and vacuum dried to obtain the micron-sized one-dimensional covalent organic framework material.

[0033] According to the present invention, preferably, the molar ratio of the highly symmetrical 3,6-di(4-formaldehydephenyl)carbazole with a 90° angle to the highly symmetrical 5,10,15,20-tetrakis(4-aminophenyl)porphyrin with a 90° angle is (1.5-2.5):1.

[0034] According to the present invention, preferably, the third solvent is at least one of 1,2-dichlorobenzene, 1-butanol, 1,3,5-trimethylbenzene, 1,4-dioxane and ethanol.

[0035] According to the present invention, preferably, the second catalyst is an aqueous acetic acid solution, the concentration of the aqueous acetic acid solution is 0.1-8 mol / L, and the ratio of the added volume of the aqueous acetic acid solution to the total volume of the solution for the Schiff base reaction is (1-3):10.

[0036] According to the present invention, preferably, in step (3):

[0037] The temperature of the Schiff base reaction is 110-130°C and the time is 70-75h;

[0038] The washing solvent used for washing is at least one of N,N-dimethylformamide, pure water, anhydrous ethanol and acetone;

[0039] The vacuum drying temperature is 70-100°C and the time is 10-16h.

[0040] In the present invention, in the step (2), as a preferred embodiment, the liquid nitrogen degassing and sealing treatment includes: sequentially freezing the equipment containing the mixed uniform solution of the step (1) with liquid nitrogen, evacuating, thawing and filling with nitrogen, and cycling for 3-4 times; then, freezing the equipment with liquid nitrogen, and sealing the equipment under evacuation. Then, after the overall temperature of the sealed equipment reaches room temperature, it is placed in an oven at 120°C for Schiff base reaction for 3 days. In the present invention, the equipment containing the mixed uniform solution of the step (1) is a high vacuum valve solvent storage bottle (volume of about 5 mL, length of 20 cm, diameter of 1 cm)

[0041] The beneficial effects of the technical solution of the present invention are as follows:

[0042] The present invention selects highly symmetrical 3,6-di(4-formylphenyl)carbazole with a 90° angle and 5,10,15,20-tetra(4-aminophenyl)porphyrin with a 90° angle, and obtains a one-dimensional covalent organic framework material through a Schiff base reaction. The material is connected by strong covalent bonds and is a linear porous organic material with diamond-shaped channels. The present invention obtains a nanoscale one-dimensional covalent organic framework material (i.e., a one-dimensional covalent organic framework material processable solution) by suppressing the speed of generating imine bonds by the Schiff base reaction.

[0043] The present invention synthesizes a one-dimensional chain covalent organic framework material by selecting a suitable solvent ratio, and the material has high crystallinity and good repeatability. The present invention adopts a method for inhibiting the speed of generating imine bonds by Schiff base reaction, and the size of the one-dimensional covalent organic framework material can be controlled at the nanometer level, thereby obtaining a one-dimensional covalent organic framework material processable solution. The one-dimensional covalent organic framework material processable solution of the present invention can be used to conveniently prepare thin films, coatings, nanoparticles and composite materials, which is convenient in energy storage and conversion, catalysis, gas separation and storage, optoelectronic materials, and biomedical fields, providing new possibilities and having broad application prospects.

[0044] Other features and advantages of the present invention will be described in detail in the following detailed description. BRIEF DESCRIPTION OF THE DRAWINGS

[0045] The above and other objects, features and advantages of the present invention will become more apparent through a more detailed description of exemplary embodiments of the present invention with reference to the accompanying drawings.

[0046] Figure 1 A transmission electron microscope image of a nanoscale one-dimensional covalent organic framework material N-TACD-COF provided in Example 1 of the present invention is shown.

[0047] Figure 2 The X-ray diffraction pattern of a micron-scale one-dimensional covalent organic framework material B-TACD-COF provided in Example 2 of the present invention ("Intensity-intensity", "2θ (degree)-Bragg angle", "Experimental-experimental data", "Pawley refined-Pauli refined data", "Simulated-simulated data", "Difference-difference data", "Bragg peak-Bragg peak", "R wp -Weighted graph variance factor", "R p -Graph variance factor”).

[0048] Figure 3A scanning electron microscope image of a micrometer-scale one-dimensional covalent organic framework material B-TACD-COF provided in Example 2 of the present invention is shown. DETAILED DESCRIPTION

[0049] The preferred embodiments of the present invention will be described in more detail below. Although the preferred embodiments of the present invention are described below, it should be understood that the present invention can be implemented in various forms and should not be limited by the embodiments set forth herein. On the contrary, these embodiments are provided to make the present invention more thorough and complete, and to fully convey the scope of the present invention to those skilled in the art.

[0050] Example 1

[0051] This embodiment provides a nanoscale one-dimensional covalent organic framework material N-TACD-COF, and the preparation method thereof comprises the following steps:

[0052] S1: 3,6-di(4-formylphenyl)carbazole (11.3 mg, 0.03 mmol) with a high symmetry and an angle of 90° and 0.2 mL of N,N-dimethylacetamide were mixed and stirred at 95°C for 15 min to obtain a mixed solution a;

[0053] S2: Highly symmetrical 5,10,15,20-tetrakis(4-aminophenyl)porphyrin (10.1 mg, 0.015 mmol) with a 90° angle, 0.7 mL of N,N-dimethylacetamide, 0.09 mL of deionized water and diglycolic acid (4.02 mg, 0.03 mmol) were mixed and stirred at 95°C for 15 min to obtain a mixed solution b;

[0054] S3: Add the mixed solution a dropwise into the mixed solution b, mix and stir evenly, and perform Schiff base reaction at 95°C for 15 minutes to obtain solution c; while hot, mix 0.1 mL of solution c with 2 mL of ethanol evenly, and age for 24 hours to obtain the nanoscale one-dimensional covalent organic framework material N-TACD-COF.

[0055] Example 2

[0056] This embodiment provides a micron-scale one-dimensional covalent organic framework material B-TACD-COF, and the preparation method thereof comprises the following steps:

[0057] (1) 3,6-di(4-formaldehydephenyl)carbazole (11.3 mg, 0.03 mmol) with high symmetry and an angle of 90°, 5,10,15,20-tetrakis(4-aminophenyl)porphyrin (10.1 mg, 0.015 mmol) with high symmetry and an angle of 90°, 0.8 mL of 1,2-dichlorobenzene, and 0.2 mL of 1-butanol were mixed and sonicated for 10 min to obtain a mixed solution 1; the mixed solution 1 was mixed with 0.1 mL of a 6 M acetic acid aqueous solution and sonicated for 10 min to obtain a mixed uniform solution;

[0058] (2) The equipment containing the mixed uniform solution of step (1) is subjected to liquid nitrogen degassing and sealing treatment. Specifically, the equipment containing the mixed uniform solution of step (1) is sequentially subjected to 77K liquid nitrogen freezing, vacuuming to 0 mbar, thawing and filling with nitrogen, and the cycle is repeated 3 times; then, the equipment is placed in liquid nitrogen freezing, and the equipment is sealed in a vacuum state; the equipment containing the mixed uniform solution of step (1) is a high vacuum valve solvent storage bottle (volume about 5 mL, length 20 cm, diameter 1 cm);

[0059] (3) After the overall temperature of the sealed device reaches room temperature, it is placed in an oven at 120° C. for Schiff base reaction for 3 days to obtain a precipitate, which is filtered and washed three times with N,N-dimethylformamide, pure water, and acetone, respectively, and vacuum dried at 75° C. for 12 h to obtain the micron-sized one-dimensional covalent organic framework material B-TACD-COF (dark brown powder).

[0060] The embodiments of the present invention have been described above, and the above description is exemplary, not exhaustive, and is not limited to the disclosed embodiments. Many modifications and changes will be apparent to those skilled in the art without departing from the scope and spirit of the described embodiments.

Claims

1. A one-dimensional covalent organic framework material, characterized in that: The one-dimensional covalent organic framework material is obtained by generating imine bonds through Schiff base reaction of highly symmetrical 3,6-di(4-formaldehydephenyl)carbazole with a 90° angle and highly symmetrical 5,10,15,20-tetra(4-aminophenyl)porphyrin with a 90° angle under solvent and catalyst conditions.

2. The one-dimensional covalent organic framework material according to claim 1, wherein The structural formula of the one-dimensional covalent organic framework material is as follows:

3. The one-dimensional covalent organic framework material according to claim 1, wherein The size of the one-dimensional covalent organic framework material is nanometer scale.

4. The one-dimensional covalent organic framework material according to claim 3, wherein: The preparation method of the nanoscale one-dimensional covalent organic framework material comprises the following steps: S1: mixing and stirring the highly symmetrical 3,6-di(4-formaldehydephenyl)carbazole and the first solvent having an angle of 90° to obtain a mixed solution a; S2: Mix and stir the highly symmetrical 5,10,15,20-tetrakis(4-aminophenyl)porphyrin with an angle of 90°, the second solvent and the first catalyst to obtain a mixed solution b; S3: The mixed solution a and the mixed solution b are mixed and stirred uniformly and subjected to a Schiff base reaction to obtain a solution c; the solution c is mixed uniformly with ethanol and subjected to an aging treatment to obtain the nanoscale one-dimensional covalent organic framework material.

5. The one-dimensional covalent organic framework material according to claim 4, wherein The molar ratio of highly symmetrical 3,6-di(4-formylphenyl)carbazole with a 90° angle, highly symmetrical 5,10,15,20-tetrakis(4-aminophenyl)porphyrin with a 90° angle and the first catalyst is (1.5-2.5):1:(1.5-2.5); The first solvent and the second solvent are each independently at least one of 1,2-dichlorobenzene, 1-butanol, 1,3,5-trimethylbenzene, 1,4-dioxane, N,N-dimethylacetamide, ethanol and water; The first catalyst is at least one of diglycolic acid, acetic acid and glutaric acid.

6. The one-dimensional covalent organic framework material according to claim 4, wherein In step S1, the mixing and stirring temperature is 80-100° C. and the time is 5-20 min; In step S2, the mixing and stirring temperature is 80-100° C. and the time is 5-20 min; In step S3: The temperature of the Schiff base reaction is 80-100°C and the time is 5-20 minutes; The volume ratio of the solution c to ethanol is (10-200): (1000-5000); The aging treatment time is 20-40h.

7. The one-dimensional covalent organic framework material according to claim 1, wherein: The size of the one-dimensional covalent organic framework material is micron-scale.

8. The one-dimensional covalent organic framework material according to claim 7, wherein: The preparation method of micron-scale one-dimensional covalent organic framework material comprises the following steps: (1) ultrasonically mixing highly symmetrical 3,6-di(4-formaldehydephenyl)carbazole having an angle of 90°, highly symmetrical 5,10,15,20-tetrakis(4-aminophenyl)porphyrin having an angle of 90°, a third solvent, and a second catalyst to obtain a uniform mixed solution; (2) degassing and sealing the equipment containing the mixed uniform solution of step (1) with liquid nitrogen; (3) subjecting the mixed uniform solution in the device treated in step (2) to a Schiff base reaction to obtain a precipitate, which is then filtered, washed and vacuum dried to obtain the micron-sized one-dimensional covalent organic framework material.

9. The one-dimensional covalent organic framework material according to claim 8, wherein: The molar ratio of the highly symmetrical 3,6-di(4-formylphenyl)carbazole with a 90° angle and the highly symmetrical 5,10,15,20-tetrakis(4-aminophenyl)porphyrin with a 90° angle is (1.5-2.5):1; The third solvent is at least one of 1,2-dichlorobenzene, 1-butanol, 1,3,5-trimethylbenzene, 1,4-dioxane and ethanol; The second catalyst is an acetic acid aqueous solution, the concentration of the acetic acid aqueous solution is 0.1-8 mol / L, and the ratio of the added volume of the acetic acid aqueous solution to the total volume of the solution for the Schiff base reaction is (1-3):

10.

10. The one-dimensional covalent organic framework material according to claim 8, wherein: In step (3): The temperature of the Schiff base reaction is 110-130°C and the time is 70-75h; The washing solvent used for washing is at least one of N,N-dimethylformamide, pure water, anhydrous ethanol and acetone; The vacuum drying temperature is 70-100°C and the time is 10-16h.

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