Application of covalent organic framework in iodine vapor adsorption

Abstract

The invention relates to the technical field of adsorption materials, and provides an application of a covalent organic framework in iodine vapor adsorption, including an application of compounds as shown in formulas 1-8 in iodine vapor adsorption. Compared with the prior art, the method has the advantages that the iodine elementary substance can be effectively adsorbed by utilizing the advantages of high porosity, high specific surface area, abundant nitrogen atoms in a framework and the like of COFs, so that the problem of recovery and treatment of the radioactive iodine elementary substance in the nuclear waste is solved, and the harm of radioactive iodine to human is reduced. Moreover, the compounds as shown in the formulas 1-8 contain light elements such as C, H, O and N, and the dosage of the compounds is smaller when the compounds adsorb the same iodine.

Description

Technical Field

[0001] The adsorption material of the present invention relates to the technical field, and more specifically, to the application of a covalent organic framework in the adsorption of iodine vapor. Background Art

[0002] The depletion of traditional fossil fuels and the pollution they cause to the environment have attracted global attention. Although nuclear energy, as a clean energy source, has been favored by many countries, its potential radioactive pollution has limited its widespread application. Radioactive iodine is one of the inevitable products of nuclear fission. If it is released into the environment, it will cause serious damage to organisms and the environment. In nuclear explosions and reactor accidents, radioactive iodine is the main nuclide that pollutes the environment in the early stage. Among the radioactive isotopes of iodine, iodine-131 and iodine-129 are relatively toxic radionuclides, especially iodine-129, which has a longer half-life and will selectively concentrate in the thyroid gland when it enters the blood, causing thyroid damage. However, due to its radioactivity, iodine is also widely used in nuclear medicine diagnosis, such as imaging of the thyroid gland, thyroid cancer metastases, or neuroectodermal tumors. At present, in the field of nuclear medicine treatment, in addition to using radioactive sodium iodide (iodine-131) to treat hyperthyroidism and thyroid cancer, new dosage forms can also be used to treat liver cancer.

[0003] Common methods for removing radioactive iodine can be divided into two categories: wet method and dry method. The wet method uses solvents to wash iodine from the gas, including alkaline washing, electrolytic washing, mercurization and iodination processes, fluorocarbon absorption, etc., to remove radioactive iodine from the exhaust gas through disproportionation reaction. The dry method mainly uses solid adsorbents to directly adsorb radioactive iodine. Due to the advantages of solid adsorbents such as simple operation, high reliability, and low maintenance and operating costs, it is considered to be an effective method for capturing volatile pollutants from exhaust gas. Traditional adsorbents are mainly activated carbon, metal exchange zeolites, aerogels, metal organic frameworks, etc., but these materials are greatly restricted in practical application due to their own limitations and low adsorption capacity. Summary of the invention

[0004] In view of this, the purpose of the present invention is to provide the application of a covalent organic framework in the adsorption of iodine vapor. The compounds represented by Formula 1 to Formula 8 of the present invention contain light elements such as C, H, O, and N, and can adsorb the same amount of iodine with less usage.

[0005] In order to achieve the above object, the present invention adopts the following technical solutions:

[0006] Application of compounds represented by formula 1 to formula 8 in adsorbing iodine vapor;

[0007]

[0008]

[0009]

[0010]

[0011]

[0012]

[0013]

[0014] The compounds shown in Formula 1 to Formula 8 are covalent organic frameworks (COFs), which are crystalline porous polymers formed by covalently connecting molecular building blocks of pre-designed geometric shapes. Due to their good chemical adjustability, structural diversity and excellent stability, they have become a promising class of nanoporous materials. Compared with traditional adsorption materials, COFs have unique properties and structural diversity, crystallinity, high surface area, adjustable pore size, thermal stability and low density. They have important application value in the fields of gas storage, gas separation, light conduction and catalysis. Based on the many advantages of COFs.

[0015] Preferably, the adsorption is carried out at 75°C.

[0016] The preparation method of the compound represented by Formula 1 comprises: mixing TAPA, TFPPy, acetic acid and o-dichlorobenzene, freezing and sealing the system at 77K; then, reacting the system at 140-160°C for 3-5d, and drying to obtain the compound represented by Formula 1.

[0017] Preferably, the preparation method of the compound shown in Formula 2 comprises: mixing TTF-4CHO, TAPA, o-dichlorobenzene and acetic acid, freezing and sealing the system at 77K; then, reacting the system at 120-140°C for 3-5d, and drying to obtain the compound shown in Formula 2.

[0018] Preferably, the preparation method of the compound represented by Formula 3 comprises: mixing TBAP, TAPA, o-dichlorobenzene and acetic acid, freezing and sealing the system at 77K; then, reacting the system at 120-140°C for 3-5d, and drying to obtain the compound represented by Formula 3.

[0019] Preferably, the preparation method of the compound shown in Formula 4 comprises: mixing terephthalaldehyde, tetraaminobenzylmethane, 1,4-dioxane and acetic acid, freezing and sealing the system at 77K; then, reacting the system at 120-140°C for 3-5d, and drying to obtain the compound shown in Formula 4.

[0020] Preferably, the preparation method of the compound represented by Formula 5 comprises: mixing PyTTA, terephthalaldehyde, 1,4-dioxane, acetic acid and mesitylene, freezing and sealing the system at 77K; then, reacting the system at 120-140°C for 3-5d, and drying to obtain the compound represented by Formula 5.

[0021] Preferably, the preparation method of the compound represented by Formula 6 comprises: mixing 2,4,6-trihydroxy-1,3,5-benzenetricarboxaldehyde, 4,4'-azodiphenylamine, 1,4-dioxane and acetic acid, reacting at 20-25° C. for 7 days, and drying to obtain the compound represented by Formula 6.

[0022] Preferably, the preparation method of the compound represented by Formula 7 comprises: mixing terephthalaldehyde, TAPA, o-dichlorobenzene and acetic acid, freezing and sealing the system at 77K; then, reacting the system at 120-140°C for 3-5d, and drying to obtain the compound represented by Formula 7.

[0023] Preferably, the preparation method of the compound shown in Formula 8 comprises: mixing tetrakis-(p-aminophenyl)porphyrin, 2,5-dihydroxyterephthalaldehyde, o-dichlorobenzene, n-butanol and acetic acid, evacuating the system to below 4 Pa, sealing the system, and reacting at 120-140° C. for 3-5 days to obtain the compound shown in Formula 8.

[0024] Preferably, the preparation method of the compound represented by Formula 1 comprises: weighing TAPA (0.1-0.10 mmol) and TFPPy (0.01-0.10 mmol) in a corresponding proportion into a 10×8 mm (od×id) Pyrex tube, adding o-dichlorobenzene (0.5-5.0 mL) into the tube, freezing the solvent part in liquid nitrogen at 77K, and after the solvent is completely frozen, adding 6M acetic acid (0.1-0.5 mL) into the tube, freezing again, and placing the Pyrex tube in liquid nitrogen at 77K for freeze degassing, repeating this step three times, and sealing the tube at high temperature with a flame gun. After the system completely returns to room temperature, it is transferred to a constant temperature oven at 160°C and allowed to react for 5 days. After the reaction is completed, the reaction system is cooled to room temperature, and the reactants are successively washed by centrifugation with dry N,N-dimethylformamide until the supernatant is clear and colorless, and then soaked in dry N,N-dimethylformamide solution overnight, and then replaced with dry tetrahydrofuran solution and continued to soak overnight, filtered, washed with dry acetone 3 times and soaked for 1-2 minutes, and the filter cake is transferred to a vacuum drying tube, heated to 120°C and vacuum dried overnight to obtain COF-602.

[0025] Preferably, the preparation method of the compound represented by Formula 2 comprises: weighing TAPA (0.1-0.10 mmol) and TTF-4CHO- (0.01-0.10 mmol) in a corresponding proportion into a 10×8 mm (od×id) Pyrex tube, adding o-dichlorobenzene (0.5-5.0 mL) into the tube, freezing the solvent part in liquid nitrogen at 77K, and after the solvent is completely frozen, adding 6M acetic acid (0.1-0.5 mL) into the tube, freezing again, and placing the Pyrex tube in liquid nitrogen at 77K for freeze degassing, repeating the cycle about three times, and sealing the tube at high temperature with a flame gun. After the system completely returns to room temperature, it is transferred to a constant temperature oven at 140°C and allowed to react for 5 days. After the reaction is completed, the reaction system is cooled to room temperature, and the reactants are successively washed by centrifugation with dry N,N-dimethylformamide until the supernatant is clear and colorless, and then soaked in dry N,N-dimethylformamide solution overnight, and then replaced with dry tetrahydrofuran solution and continued to soak overnight, filtered, washed with dry acetone 3 times and soaked for 1-2 minutes, and the filter cake is transferred to a vacuum drying tube, heated to 120°C and vacuum dried overnight to obtain 3DCOF-TTF-Ad.

[0026] Preferably, the preparation method of the compound represented by Formula 3 comprises: weighing TAPA (0.1-0.10 mmol) and TBAP (0.01-0.10 mmol) in a corresponding proportion into a 10×8 mm (od×id) Pyrex tube, adding o-dichlorobenzene (0.5-5.0 mL) into the tube, freezing the solvent part in liquid nitrogen at 77K, and after the solvent is completely frozen, adding 6M acetic acid (0.1-0.5 mL) into the tube, freezing again, and placing the Pyrex tube in liquid nitrogen at 77K for freeze degassing, repeating the cycle for about three times, and sealing the tube at high temperature with a flame gun. After the system completely returns to room temperature, it is transferred to a constant temperature oven at 140°C and allowed to react for 5 days. After the reaction is completed, the reaction system is cooled to room temperature, and the reactants are successively washed by centrifugation with dry N,N-dimethylformamide until the supernatant is clear and colorless, and then soaked in dry N,N-dimethylformamide solution overnight, and then replaced with dry tetrahydrofuran solution and continued to soak overnight, filtered, washed with dry acetone 3 times and soaked for 1-2 minutes, and the filter cake is transferred to a vacuum drying tube, heated to 120°C and vacuum dried overnight to obtain 3DCOF-TBAP.

[0027] Preferably, the preparation method of the compound shown in Formula 4 comprises: weighing terephthalaldehyde (TPA, 0.02-0.20 mmol), tetraaminobenzyl methane (TAM, 0.01-0.40 mmol) in a 10 mL Pyrex tube, and then adding 0.5-5 mL of anhydrous dioxane. The solvent-containing part of the lower end of the Pyrex tube is placed in liquid nitrogen at 77K for freezing, and then 0.2-1.0 mL of 6MAcOH is added, and it is placed in a liquid nitrogen environment for continued freezing, and vacuum-filled with nitrogen for three times to deoxygenate, and sealed with a high-temperature flame. After the Pyrex tube completely returns to room temperature, it is transferred to a constant temperature oven at 120°C and allowed to react for 72 hours. After the reaction is completed, it is cooled to room temperature, and the product is fully washed with dry dioxane and THF for 3-5 times. The product is then soaked in a dry THF solution for about 24 hours. The solid product is filtered and vacuum dried at 100°C overnight to obtain COF-300.

[0028] Preferably, the preparation method of the compound represented by Formula 5 comprises: weighing PyTTA (0.01-0.10 mmol) and terephthalaldehyde (TPA) (0.02-0.20 mmol) in sequence and adding them to a Pyrex tube. Take 0.3-1.5 mL of 1,4-dioxane and 0.6-3.0 mL of mesitylene and add them to the Pyrex tube, and ultrasonicate to evenly disperse the solid. Take 0.1-0.5 mL of 6M acetic acid and add it to the Pyrex tube, and continue ultrasonicating for 1-5 min. After the ultrasonication stops, place the Pyrex tube in liquid nitrogen, freeze and degas, repeat 3 times, and vacuum seal the tube with a flame gun. After cooling it to room temperature, place it in a 120°C room temperature drying oven and react for 3 days. After the reaction stops, take out the Pyrex tube, wait for it to cool to room temperature, break it, add a small amount of tetrahydrofuran (THF), filter it, and collect the solid. After washing the solid with THF, continue soaking it in THF for 2 days, filter and collect the solid, and dry the solid in vacuum at 120°C overnight to obtain yellow-brown powder COF-Py-1P.

[0029] Preferably, the preparation method of the compound represented by Formula 6 comprises: weighing 2,4,6-trihydroxy-1,3,5-benzenetricarboxaldehyde (TP) (0.02-0.10 mmol) and 4,4'-azodiphenylamine (Azo) (0.03-0.15 mmol) in sequence, and adding them to a 5 mL sample bottle. Take 1-5 mL of 1,4-dioxane and add it to the sample bottle, and ultrasonicate to evenly disperse the solid. Take 0.1-0.5 mL of 6M acetic acid and add it to the sample bottle, and continue ultrasonicating for 1-5 minutes. After the ultrasonication stops, place the sample bottle in a fume hood and let it stand for 7 days. After the reaction stops, open the sample bottle, add a small amount of N,N-dimethylformamide (DMF), filter and collect the solid. Wash the solid with DMF, soak it in DMF until the supernatant is colorless, continue to soak it in tetrahydrofuran (THF) for 2 days, filter and collect the solid. The solid was dried at 150 °C in vacuum overnight to obtain red powder COF-TP-Azo.

[0030] Preferably, the preparation method of the compound represented by Formula 7 comprises: weighing terephthalaldehyde (TPA 0.1-0.5 mmol) and TAPA (0.02-0.5 mmol) into a 10×8 mm (od×id) Pyrex tube, adding o-dichlorobenzene (1.0-5.0 mL) into the tube, freezing the solvent part in liquid nitrogen at 77K, and after the solvent is completely frozen, adding 6M acetic acid (0.1-0.5 mL) into the tube, freezing again, and placing the Pyrex tube in liquid nitrogen at 77K for freeze degassing, repeating the cycle about three times, and sealing the tube at high temperature with a flame gun. After the system completely returns to room temperature, it is transferred to a constant temperature oven at 140°C and allowed to react for 5 days. After the reaction is completed, the reaction system is cooled to room temperature, and the reactants are successively washed by centrifugation with dry N,N-dimethylformamide until the supernatant is clear and colorless, and then soaked overnight with dry N,N-dimethylformamide solution, and then replaced with dry tetrahydrofuran solution and continued to soak overnight, filtered, washed 3 times with dry acetone and soaked for 1 to 5 minutes, and the filter cake is transferred to a vacuum drying tube, heated to 120°C and vacuum dried overnight to obtain COF-229.

[0031] Preferably, the preparation method of the compound represented by Formula 8 comprises: taking tetrakis-(p-aminophenyl)porphyrin (TAPP 0.01-0.10 mmol) and 2,5-dihydroxyterephthalaldehyde (Dha 0.02-0.20 mmol) and adding them into a Pyrex tube, then adding 1-5 mL of o-dichlorobenzene / n-butanol / (volume ratio is 1 / 1), sealing and ultrasonicating for 6 minutes to make the monomer well dispersed in the solvent, freezing the reaction tube in liquid nitrogen, and then adding 0.2-1.0 mL of 6M AcOH, vacuuming, filling with nitrogen, and freezing and thawing three times, and then vacuuming to below 4 Pa ​​after freezing in liquid nitrogen, flame sealing and placing in a 120° C. oven for reaction for 72 hours, washing three times with THF after the reaction, and then soaking in THF for 2 days, DMF for 1 day, and then changing to acetone for soaking for 2 days, and finally obtaining a purple powder as THPP-COF.

[0032] The present invention has the following advantages:

[0033] 1. Compared with the existing adsorption methods, the method adopted by the present invention is simple, effective and safe.

[0034] 2. The present invention adopts two small vials to respectively contain COFs and iodine, with appropriate dosage and small error. There is almost no loss of iodine and COFs materials, and they are easy to recycle.

[0035] 3. Compared with other materials, under the same conditions, after COFs adsorb iodine, they have better stability due to their own skeleton characteristics.

[0036] 4. The present invention utilizes the advantages of COFs such as high porosity, high specific surface area and abundant nitrogen atoms in the framework to effectively adsorb and recover iodine, thereby solving the difficult problems of recovery and treatment of radioactive iodine in nuclear waste and reducing the harm of radioactive iodine to humans.

[0037] 5. Compared with other materials, COFs mainly contain light elements such as C, H, O, and N, and can adsorb the same amount of iodine with less usage. BRIEF DESCRIPTION OF THE DRAWINGS

[0038] Figure 1 1 is the isothermal adsorption curve of iodine adsorption by COF of Examples 1-8. DETAILED DESCRIPTION

[0039] The technical solution of the present invention will be clearly and completely described below in conjunction with the embodiments of the present invention. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0040] In order to further illustrate the present invention, the following examples are used to describe the present invention in detail. The raw materials used in the following examples of the present invention are all commercially available products.

[0041] The covalent organic framework used in the following embodiments of the present invention is as follows:

[0042]

[0043]

[0044]

[0045]

[0046]

[0047]

[0048]

[0049] The preparation method of the above compound is as follows:

[0050] The preparation method of formula 1 (COF-602) includes: weighing TAPA (0.1-0.10 mmol) and a corresponding proportion of TFPPy (0.01-0.10 mmol) into a 10×8 mm (od×id) Pyrex tube, adding o-dichlorobenzene (0.5-5.0 mL) into the tube, freezing the solvent part in liquid nitrogen at 77K, and after the solvent is completely frozen, adding 6M acetic acid (0.1-0.5 mL) into the tube, freezing again, and placing the Pyrex tube in liquid nitrogen at 77K for freeze degassing, repeating this step three times, taking the system out of the liquid nitrogen, and sealing the tube at high temperature with a flame gun. Subsequently, the system was taken out from the liquid nitrogen, and after the system completely returned to room temperature, it was transferred to a constant temperature oven at 160°C and allowed to react for 5 days. After the reaction was completed, the reaction system was cooled to room temperature, and the reactants were successively washed by centrifugation with dry N,N-dimethylformamide until the supernatant was clear and colorless, and then soaked in dry N,N-dimethylformamide solution overnight, and then replaced with dry tetrahydrofuran solution and continued to soak overnight, filtered, washed with dry acetone 3 times and soaked for 1-2 minutes, and the filter cake was transferred to a vacuum drying tube, heated to 120°C and vacuum dried overnight to obtain COF-602.

[0051] The preparation method of formula 2 (COF-TTF-Ad) comprises: weighing TAPA (0.1-0.10 mmol) and TTF-4CHO- (0.01-0.10 mmol) in a corresponding proportion into a 10×8 mm (od×id) Pyrex tube, adding o-dichlorobenzene (0.5-5.0 mL) into the tube, freezing the solvent part in liquid nitrogen at 77K, and after the solvent is completely frozen, adding 6M acetic acid (0.1-0.5 mL) into the tube, freezing again, and placing the Pyrex tube in liquid nitrogen at 77K for freeze degassing, repeating the cycle about three times, taking the system out of the liquid nitrogen, and sealing the tube at high temperature with a flame gun. Subsequently, the system was taken out from the liquid nitrogen, and after the system completely returned to room temperature, it was transferred to a constant temperature oven at 140°C and allowed to react for 5 days. After the reaction was completed, the reaction system was cooled to room temperature, and the reactants were successively washed by centrifugation with dry N,N-dimethylformamide until the supernatant was clear and colorless, and then soaked in dry N,N-dimethylformamide solution overnight, and then replaced with dry tetrahydrofuran solution and continued to soak overnight, filtered, washed with dry acetone 3 times and soaked for 1-2 minutes, and the filter cake was transferred to a vacuum drying tube, heated to 120°C and vacuum dried overnight to obtain 3D COF-TTF-Ad.

[0052] The preparation method of formula 3 (COF-TBAP) comprises: weighing TAPA (0.1-0.10 mmol) and TBAP (0.01-0.10 mmol) in a corresponding proportion into a 10×8 mm (od×id) Pyrex tube, adding o-dichlorobenzene (0.5-5.0 mL) into the tube, freezing the solvent part in liquid nitrogen at 77K, and after the solvent is completely frozen, adding 6M acetic acid (0.1-0.5 mL) into the tube, freezing again, and placing the Pyrex tube in liquid nitrogen at 77K for freeze degassing, repeating the cycle about three times, taking the system out of the liquid nitrogen, and sealing the tube at high temperature with a flame gun. Subsequently, the system was taken out of liquid nitrogen, and after the system completely returned to room temperature, it was transferred to a constant temperature oven at 140°C and allowed to react for 5 days. After the reaction was completed, the reaction system was cooled to room temperature, and the reactants were successively washed by centrifugation with dry N,N-dimethylformamide until the supernatant was clear and colorless, and then soaked in dry N,N-dimethylformamide solution overnight, and then replaced with dry tetrahydrofuran solution and continued to soak overnight, filtered, washed with dry acetone 3 times and soaked for 1-2 minutes, and the filter cake was transferred to a vacuum drying tube, heated to 120°C and vacuum dried overnight to obtain 3D COF-TBAP.

[0053] The preparation method of formula 4 (COF-300) includes: weighing terephthalaldehyde (TPA, 0.02-0.20 mmol), tetraaminobenzylmethane (TAM, 0.01-0.40 mmol) in a 10 mL Pyrex tube, and then adding 0.5-5 mL of anhydrous 1,4-dioxane. The solvent-containing part of the lower end of the Pyrex tube is placed in liquid nitrogen at 77K for freezing, and then 0.2-1.0 mL of 6MAcOH is added, and the system is placed in a liquid nitrogen environment for continued freezing, and the system is removed from the liquid nitrogen by vacuuming and filling with nitrogen three times for deoxygenation, and the system is removed from the liquid nitrogen and sealed with a high-temperature flame. Subsequently, the system is removed from the liquid nitrogen, and after the Pyrex tube is completely restored to room temperature, it is transferred to a constant temperature oven at 120°C and allowed to react for 72 hours. After the reaction is completed, it is cooled to room temperature, and the product is fully washed with dry dioxane and THF for 3-5 times. The product is then soaked in a dry THF solution for about 24 hours. The solid product was filtered off and dried under vacuum at 100°C overnight to obtain COF-300.

[0054] The preparation method of formula 5 (COF-Py-1P) includes: weighing PyTTA (0.01-0.10 mmol) and terephthalaldehyde (TPA) (0.02-0.20 mmol) in turn and adding them to a Pyrex tube. Take 0.3-1.5 mL of 1,4-dioxane and 0.6-3.0 mL of mesitylene and add them to the Pyrex tube, and ultrasonicate to make the solid dispersed evenly. Take 0.1-0.5 mL of 6M acetic acid and add it to the Pyrex tube, and continue ultrasonicating for 1-5 minutes. After the ultrasonication stops, put the Pyrex tube in liquid nitrogen at 77K, freeze and degas, repeat 3 times, take out the system from the liquid nitrogen, and vacuum seal the tube with a flame gun. Subsequently, take out the system from the liquid nitrogen, wait for it to cool to room temperature, and then put it into a 120°C room temperature drying oven for reaction for 3 days. After the reaction stops, take out the Pyrex tube, wait for it to cool to room temperature, break it, add a small amount of tetrahydrofuran (THF), filter and collect the solid. After washing the solid with THF, continue to soak it in THF for 2 days, filter and collect the solid. Dry the solid in vacuum at 120°C overnight to obtain yellow-brown powder COF-Py-1P.

[0055] The preparation method of formula 6 (COF-TP-Azo) includes: weighing 2,4,6-trihydroxy-1,3,5-benzenetricarboxaldehyde (TP) (0.02-0.10 mmol) and 4,4'-azodiphenylamine (Azo) (0.03-0.15 mmol) in sequence, and adding them to a 5 mL sample bottle. Take 1-5 mL of 1,4-dioxane and add it to the sample bottle, and ultrasonicate to evenly disperse the solid. Take 0.1-0.5 mL of 6M acetic acid and add it to the sample bottle, and continue ultrasonicating for 1-5 minutes. After the ultrasonication stops, put the sample bottle in a fume hood and let it stand for 7 days. After the reaction stops, open the sample bottle, add a small amount of N,N-dimethylformamide (DMF), filter and collect the solid. Wash the solid with DMF, soak it with DMF until the supernatant is colorless, continue to soak it with tetrahydrofuran (THF) for 2 days, filter and collect the solid. The solid was dried at 150 °C in vacuum overnight to obtain red powder COF-TP-Azo.

[0056] The preparation method of formula 7 (COF-229) comprises: weighing terephthalaldehyde (TPA 0.1-0.5 mmol) and TAPA (0.02-0.5 mmol) into a 10×8 mm (od×id) Pyrex tube, adding o-dichlorobenzene (1.0-5.0 mL) into the tube, freezing the solvent part in liquid nitrogen at 77K, and after the solvent is completely frozen, adding 6M acetic acid (0.1-0.5 mL) into the tube, freezing again, and placing the Pyrex tube in liquid nitrogen at 77K for freeze degassing, repeating the cycle about three times, taking the system out of the liquid nitrogen, and sealing the tube at high temperature with a flame gun. After the system completely returns to room temperature, it is transferred to a constant temperature oven at 140°C and allowed to react for 5 days. After the reaction is completed, the reaction system is cooled to room temperature, and the reactants are successively washed by centrifugation with dry N,N-dimethylformamide until the supernatant is clear and colorless, and then soaked overnight with dry N,N-dimethylformamide solution, and then replaced with dry tetrahydrofuran solution and continued to soak overnight, filtered, washed 3 times with dry acetone and soaked for 1 to 5 minutes, and the filter cake is transferred to a vacuum drying tube, heated to 120°C and vacuum dried overnight to obtain COF-229.

[0057] The preparation method of Formula 8 (THPP-COF) includes: taking tetrakis-(p-aminophenyl)porphyrin (TAPP 0.01-0.10mmol) and 2,5-dihydroxyterephthalaldehyde (Dha 0.02-0.20mmol) into a Pyrex tube, then adding 1-5mL of o-dichlorobenzene / n-butanol / (volume ratio is 1 / 1), sealing and ultrasonicating for 6min to make the monomer well dispersed in the solvent, freezing the reaction tube in liquid nitrogen, and then adding 0.2-1.0mL of 6MAcOH, after three times of vacuuming, nitrogen filling, and freezing and thawing, vacuuming to below 4Pa after freezing in liquid nitrogen, flame sealing the tube, and then placing the system in a 120°C oven for reaction for 72h, washing three times with THF after the reaction, and then soaking in THF for 2 days, DMF for 1 day, and then changing to acetone for soaking for 2 days, and finally obtaining a purple powder as THPP-COF.

[0058] Example 1

[0059] Iodine adsorption experiment of COF-602 (Formula 1)

[0060] Place 10 mg of COF-602 (mass is m) into a 2 mL vial (mass is m a ) and then put 0.5g of iodine into another 2mL vial ( 127 I2), and finally put the two vials into the bottom of a 20mL vial, seal the 20mL vial, put the sealed 20mL vial into a 75℃ oven, the pressure is normal pressure, and weigh the vial containing COF-602 every 3 hours (recorded as m b1 , m b2 ,…,m bn ), and the measurement was stopped until the mass of the vial containing COF-602 changed by less than 0.1 mg within three times. According to the formula (m b -m a ) / m calculated the adsorption amount corresponding to different time points and obtained the final adsorption amount to be 630.0%.

[0061] Example 2

[0062] 3D COF-TTF-Ad (Formula 2) iodine adsorption experiment

[0063] 10 mg of 3D COF-TTF-Ad (mass is m) was weighed and placed in a 2 mL vial (mass is m a ) and then put 0.5g of iodine into another 2mL vial ( 127I2), and finally put the two vials into the bottom of a 20mL vial, seal the 20mL vial, put the sealed 20mL vial into a 75℃ oven at normal pressure, and weigh the mass of the vial containing 3D COF-TTF-Ad every 3 hours (recorded as m b1 , m b2 ,…,m bn ), and the measurement was stopped until the mass of the vial containing 3D COF-TTF-Ad changed by less than 0.1 mg within three times. According to the formula (m b -m a ) / m calculated the adsorption amount corresponding to different time points and obtained the final adsorption amount to be 522.0%.

[0064] Example 3

[0065] Iodine adsorption experiment of COF-TATB-TAPA (Formula 3)

[0066] 10 mg of COF-TATB-TAPA (mass is m) was weighed and placed in a 2 mL vial (mass is m a ) and then put 0.5g of iodine into another 2mL vial ( 127 I2), and finally put the two vials into the bottom of a 20mL vial, seal the 20mL vial, put the sealed 20mL vial into a 75℃ oven, the pressure is normal pressure, and weigh the vial containing COF-TATB-TAPA every 3 hours (recorded as m b1 , m b2 ,…,m bn ), and the measurement was stopped until the mass of the vial containing COF-TATB-TAPA changed by less than 0.1 mg within three times. According to the formula (m b -m a ) / m calculated the adsorption amount corresponding to different time points and obtained the final adsorption amount to be 529.0%.

[0067] Example 4

[0068] 3D COF-320 (Formula 4) iodine adsorption experiment

[0069] 10 mg of 3D COF-320 (mass is m) was weighed and placed in a 2 mL vial (mass is m a ) and then put 0.5g of iodine into another 2mL vial ( 127 I2), and finally put the two vials into the bottom of a 20mL vial, seal the 20mL vial, put the sealed 20mL vial into a 75℃ oven at normal pressure, and weigh the mass of the vial containing 3D COF-320 (recorded as m) every 3 hours. b1 , mb2 ,…,m bn ), the measurement was stopped until the mass of the vial containing 3D COF-320 changed by less than 0.1 mg within three times. According to the formula (m b -m a ) / m calculated the adsorption amount corresponding to different time points and obtained the final adsorption amount to be 815.0%.

[0070] Example 5

[0071] Iodine adsorption experiment of Py-1P COF (Formula 5)

[0072] 10 mg of Py-1P COF (mass is m) was weighed and placed in a 2 mL vial (mass is m a ) and then put 0.5g of iodine into another 2mL vial ( 127 I2), and finally put the two vials into the bottom of a 20mL vial, seal the 20mL vial, put the sealed 20mL vial into a 75℃ oven at normal pressure, and weigh the mass of the vial containing Py-1P COF every 3 hours (recorded as m b1 , m b2 ,…,m bn ), and the measurement was stopped until the mass of the vial containing Py-1P COF changed by less than 0.1 mg within three times. According to the formula (m b -m a ) / m calculated the adsorption amount corresponding to different time points and obtained the final adsorption amount to be 370.0%.

[0073] Example 6

[0074] TP-Azo COF (Formula 6) Iodine adsorption experiment

[0075] Weigh 10 mg of TP-Azo COF (mass is m) and place it into a 2 mL vial (mass is m a ) and then put 0.5g of iodine into another 2mL vial ( 127 I2), and finally put the two vials into the bottom of a 20mL vial, seal the 20mL vial, put the sealed 20mL vial into a 75℃ oven, the pressure is normal pressure, and weigh the mass of the vial containing TP-Azo COF every 3 hours (recorded as m b1 , m b2 ,…,m bn ), and the measurement was stopped until the mass of the vial containing TP-Azo COF changed by less than 0.1 mg within three times. According to the formula (m b -m a) / m calculated the adsorption amount corresponding to different moments and obtained the final adsorption amount to be 500.0%.

[0076] Example 7

[0077] Iodine adsorption experiment of COF-229 (Formula 7)

[0078] 10 mg of COF-229 (mass is m) was weighed and placed in a 2 mL vial (mass is m a ) and then put 0.5g of iodine into another 2mL vial ( 127 I2), and finally put the two vials into the bottom of a 20mL vial, seal the 20mL vial, put the sealed 20mL vial into a 75℃ oven, the pressure is normal pressure, and weigh the vial containing COF-229 every 3 hours (recorded as m b1 , m b2 ,…,m bn ), and the measurement was stopped until the mass of the vial containing COF-229 changed by less than 0.1 mg within three times. According to the formula (m b -m a ) / m calculated the adsorption amount corresponding to different time points and obtained the final adsorption amount to be 773.0%.

[0079] Example 8

[0080] THPP-COF (Formula 8) iodine adsorption experiment

[0081] 10 mg of THPP-COF (mass is m) was weighed and placed in a 2 mL vial (mass is m a ) and then put 0.5g of iodine into another 2mL vial ( 127 I2), and finally put the two vials into the bottom of a 20mL vial, seal the 20mL vial, put the sealed 20mL vial into a 75℃ oven, the pressure is normal pressure, and weigh the mass of the vial containing THPP-COF every 3 hours (recorded as m b1 , m b2 ,…,m bn ), and the measurement was stopped until the mass of the vial containing THPP-COF changed by less than 0.1 mg within three times. According to the formula (m b -m a ) / m calculated the adsorption amount corresponding to different time points and obtained the final adsorption amount to be 712.0%.

[0082] The above description of the disclosed embodiments enables those skilled in the art to implement or use the present invention. Various modifications to these embodiments will be apparent to those skilled in the art, and the general principles defined herein may be implemented in other embodiments without departing from the spirit or scope of the present invention. Therefore, the present invention will not be limited to the embodiments shown herein, but rather to the widest scope consistent with the principles and novel features disclosed herein.

Claims

1. Application of the compounds represented by Formula 1 to Formula 8 in adsorbing iodine vapor; 2. The use according to claim 1, characterized in that: The adsorption was carried out at 75°C.

3. The use according to claim 1, characterized in that: The preparation method of the compound represented by Formula 1 comprises: mixing TAPA, TFPPy, acetic acid and o-dichlorobenzene, freezing and sealing the system at 77K; then, reacting the system at 140-160°C for 3-5d, and drying to obtain the compound represented by Formula 1.

4. The use according to claim 1, characterized in that: The preparation method of the compound shown in Formula 2 comprises: mixing TTF-4CHO, TAPA, o-dichlorobenzene and acetic acid, freezing and sealing the system at 77K; then, reacting the system at 120-140°C for 3-5d, and drying to obtain the compound shown in Formula 2.

5. The use according to claim 1, characterized in that: The preparation method of the compound shown in Formula 3 comprises: mixing TBAP, TAPA, o-dichlorobenzene and acetic acid, freezing and sealing the system at 77K; then, reacting the system at 120-140°C for 3-5d, and drying to obtain the compound shown in Formula 3.

6. The use according to claim 1, characterized in that: The preparation method of the compound shown in Formula 4 comprises: mixing terephthalaldehyde, tetraaminobenzylmethane, 1,4-dioxane and acetic acid, freezing and sealing the system at 77K; then, reacting the system at 120-140°C for 3-5d, and drying to obtain the compound shown in Formula 4.

7. The use according to claim 1, characterized in that: The preparation method of the compound represented by Formula 5 comprises: mixing PyTTA, terephthalaldehyde, 1,4-dioxane, acetic acid and mesitylene, freezing and sealing the system at 77K; then, reacting the system at 120-140°C for 3-5d, and drying to obtain the compound represented by Formula 5.

8. The use according to claim 1, characterized in that: The preparation method of the compound shown in Formula 6 comprises: mixing 2,4,6-trihydroxy-1,3,5-benzenetricarboxaldehyde, 4,4'-azodiphenylamine, 1,4-dioxane and acetic acid, reacting at 20-25° C. for 7 days, and drying to obtain the compound shown in Formula 6.

9. The use according to claim 1, characterized in that: The preparation method of the compound shown in Formula 7 comprises: mixing terephthalaldehyde, TAPA, o-dichlorobenzene and acetic acid, freezing and sealing the system at 77K; then, reacting the system at 120-140°C for 3-5d, and drying to obtain the compound shown in Formula 7.

10. The use according to claim 1, characterized in that: The preparation method of the compound shown in Formula 8 comprises: mixing tetrakis-(p-aminophenyl)porphyrin, 2,5-dihydroxyterephthalaldehyde, o-dichlorobenzene, n-butanol and acetic acid, evacuating the system to below 4 Pa, sealing the system, and reacting at 120-140° C. for 3-5 days to obtain the compound shown in Formula 8.

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