CN114163594A - Preparation of hydrazone porous covalent organic framework material containing amino functional group and application of hydrazone porous covalent organic framework material in gaseous iodine adsorption - Google Patents

Preparation of hydrazone porous covalent organic framework material containing amino functional group and application of hydrazone porous covalent organic framework material in gaseous iodine adsorption Download PDF

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CN114163594A
CN114163594A CN202111366194.3A CN202111366194A CN114163594A CN 114163594 A CN114163594 A CN 114163594A CN 202111366194 A CN202111366194 A CN 202111366194A CN 114163594 A CN114163594 A CN 114163594A
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hydrazone
organic framework
covalent organic
amino functional
framework material
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蔡松亮
汤西豪
张舒媛
章伟光
郑盛润
范军
吴佳琳
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Guangdong Longsim Biochemical Technology Co ltd
South China Normal University Qingyuan Institute of Science and Technology Innovation Co Ltd
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Guangdong Longsim Biochemical Technology Co ltd
South China Normal University Qingyuan Institute of Science and Technology Innovation Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G12/00—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen
    • C08G12/02—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes
    • C08G12/04—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes with acyclic or carbocyclic compounds
    • C08G12/22—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes with acyclic or carbocyclic compounds with carboxylic acid amides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
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    • B01D53/02—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
    • B01J20/223—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material containing metals, e.g. organo-metallic compounds, coordination complexes
    • B01J20/226—Coordination polymers, e.g. metal-organic frameworks [MOF], zeolitic imidazolate frameworks [ZIF]
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G12/00—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen
    • C08G12/02—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes
    • C08G12/04—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes with acyclic or carbocyclic compounds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2253/00—Adsorbents used in seperation treatment of gases and vapours
    • B01D2253/20—Organic adsorbents
    • B01D2253/204—Metal organic frameworks (MOF's)
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2220/00—Aspects relating to sorbent materials
    • B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
    • B01J2220/48—Sorbents characterised by the starting material used for their preparation
    • B01J2220/4812—Sorbents characterised by the starting material used for their preparation the starting material being of organic character

Abstract

The invention belongs to the technical field of covalent organic framework functional materials, and particularly relates to preparation of a hydrazone porous covalent organic framework material containing an amino functional group and application of the hydrazone porous covalent organic framework material in gaseous iodine adsorption, in order to develop an amino functional material with high-efficiency iodine adsorption performance, amino functional dihydrazide monomers containing different reactive functional groups are firstly designed and synthesized, and then the porous hydrazone porous covalent organic framework material containing the amino functional group is obtained through the protection effect of inert gas and the acetic acid catalytic reaction of 2,4,6- (4-aldehyde phenyl) -1,3, 5-triazine in an organic solvent. On one hand, the synthesis method has the advantages of simplicity, convenience, short reaction period and the like; on the other hand, the hydrazone porous covalent organic framework material obtained by synthesis contains abundant amino functional sites, has the advantages of good crystallinity, high specific surface area, high stability and the like, and can be used as an adsorption material for effectively adsorbing gaseous iodine.

Description

Preparation of hydrazone porous covalent organic framework material containing amino functional group and application of hydrazone porous covalent organic framework material in gaseous iodine adsorption
Technical Field
The invention belongs to the technical field of covalent organic framework functional materials, and particularly relates to preparation of a hydrazone porous covalent organic framework material containing an amino functional group and application of the hydrazone porous covalent organic framework material in gaseous iodine adsorption.
Background
Nuclear energy is one of the most promising clean energy sources for humans in the future. However, as the nuclear industry continues to evolve, the production of nuclear waste is increasing. In addition, the spent fuel contains a large amount of raw material uranium and a large amount of solid or gaseous radioactive elements generated by fission, and if the spent fuel is not recycled and treated, the spent fuel can cause serious harm to the ecological environment and human health. Compared with solid radioactive wastes, the gaseous radioactive wastes have larger pollution area and stronger harm because of having great fluidity and being easy to move along with the airflow. Radioactive iodine is one of the most important radioactive contaminants in gaseous radioactive nuclear waste, and exists mainly in the form of125I、129I and131i, among these isotopes of iodine,125i and131i is a relatively toxic radioactive contaminant. Radioactive iodine contaminants are the most harmful of the numerous radioactive substances. Therefore, the enrichment and storage of gaseous iodine in nuclear power plant exhaust has become the most important issue in radioactive exhaust treatment worldwide. Currently, the solid phase adsorption method is the most commonly used method for enriching and storing radioactive gas iodine, and is widely researched and applied.
Covalent Organic Frameworks (COFs) are a new class of ordered porous crystalline materials, formed by organic building blocks linked by strong covalent bonds. As one of typical representatives of novel porous materials, the COF material not only has the characteristics of regular structure, ordered pore channels, large specific surface area and the like, but also has high flexible molecular designability and pore channel structure controllability, and has good application prospect in the field of gaseous iodine adsorption. Researches show that the nitrogen-rich structure and the electron-rich pi-pi conjugated system can provide effective binding sites for iodine adsorption, and particularly the existence of a large number of nitrogen atoms can improve the iodine adsorption capacity of the material. The amino functional group is Lewis base and is a good electron-donating group, and if the amino functional group is introduced into a COF framework structure, the amino on the pore wall of the obtained COF material can provide an effective binding site for the adsorption of gaseous iodine, so that the adsorption capacity of the material to iodine is expected to be improved. Currently, common strategies for constructing amino-functionalized COF materials include the following: the first strategy is to use monomer exchange method to prepare amino-functional COF, but this strategy has long synthesis period and complicated process, and can reduce the crystallinity of COF after monomer exchange. The second strategy is to reduce the nitro-functionalized COF by post-modification to form an amino-functionalized COF material, and the second strategy also has problems that the synthesis process is complicated and the crystallinity is difficult to maintain. The third strategy is to achieve the synthesis of amino-functionalized COF by controlling the monomer stoichiometry. For example, COF materials containing amino groups are synthesized by controlling the reaction ratio of tetraamine monomers and trialdehyde monomers. However, since the four amino groups of the tetraamine monomer have the same reactivity, the target COF is formed and other byproducts are also formed.
Therefore, the amino-functionalized COF material with simple synthesis method and high nitrogen content is designed and used for iodine enrichment and storage, and has very important practical significance and application value.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention provides a hydrazone porous covalent organic framework material containing amino functional groups, which contains abundant amino functional sites, has good crystallinity, large specific surface area and high stability, can be used for gaseous iodine adsorption, has a simple and convenient synthesis method and a short period, and provides a new thought for designing an amino functional COF material with a simple synthesis method and high nitrogen content.
In order to achieve the purpose, the invention adopts the technical scheme that:
the invention provides a hydrazone porous covalent organic framework material (also called amino functional hydrazone covalent organic framework material, NH for short) containing amino functional groups2-Th-Tz COF), the hydrazone porous covalent organic framework material containing amino functional groups has a structure shown in formula (i):
Figure BDA0003360710070000021
the invention also provides a preparation method of the hydrazone porous covalent organic framework material containing the amino functional group, which comprises the following steps: under the protection of inert gas atmosphere, the amino functional dihydrazide monomer shown in the formula (II) and 2,4,6- (4-aldehyde phenyl) -1,3, 5-triazine shown in the formula (III) are subjected to acetic acid catalytic reaction in an organic solvent to prepare the compound with the structure shown in the specification:
Figure BDA0003360710070000022
the invention develops a simple synthesis way for realizing amino functional COF by controlling the reactivity of monomer functional groups. Specifically, a dihydrazide monomer containing an amino group is designed and synthesized firstly, and the reactivity of the amino group is lower than that of the hydrazide, so that a hydrazide group can preferentially participate in the construction of a COF framework when reacting with an aldehyde monomer, so that a naked amino functional group can be reserved in a COF structure, and the amino-functionalized COF material is obtained. The synthesis strategy has the advantages of simplicity, convenience, short reaction period and the like. The method for preparing the amino functionalized hydrazone covalent organic framework material is a new synthesis strategy, and the prepared hydrazone covalent organic framework material contains abundant amino functional sites, has the advantages of good crystallinity, large specific surface area, high stability and the like, and can be used for gaseous iodine adsorption.
Preferably, the molar ratio of the 2,4,6- (4-formylphenyl) -1,3, 5-triazine to the amino-functional dihydrazide monomer is 1: (1-1.5). Specifically, the molar ratio of the 2,4,6- (4-aldehyde phenyl) -1,3, 5-triazine to the amino-functionalized dihydrazide monomer is 1: 1.5.
preferably, the molar amount of acetic acid used for the acetic acid catalytic reaction is 10 to 30 times of that of the amino-functionalized dihydrazide monomer. Further, the concentration of acetic acid may be in the range generally used, and the most suitable concentration is 6 to 9M.
Preferably, the temperature of the acetic acid catalytic reaction is 90-120 ℃, and the time is 3-5 days. Specifically, the reaction temperature was 110 ℃ and the reaction time was 3 days.
Preferably, the organic solvent includes a mixed solvent of mesitylene and dioxane and a mixed solvent of mesitylene and N, N' -dimethylformamide.
Preferably, the organic solvent is a mixed solvent of mesitylene and dioxane, and the volume ratio of the mesitylene to the dioxane is 1: 1-9. Specifically, the mixing volume ratio of mesitylene and dioxane is 1: 1.
Preferably, the organic solvent is added in an amount such that the molar concentration of the amino-functional dihydrazide monomer is 0.01 to 0.03 mmol/mL. Further, the amount of the organic solvent added was such that the molar concentration of the amino-functional dihydrazide monomer was 0.03 mmol/mL.
Preferably, the reaction further comprises a post-treatment step, specifically: and cooling the reacted solution to room temperature, filtering and collecting to obtain a solid precipitate, washing the precipitate with tetrahydrofuran and absolute ethyl alcohol for several times in sequence, and finally drying to obtain the amino functionalized hydrazone covalent organic framework material.
Preferably, the inert gas includes, but is not limited to, argon.
The invention also provides application of the hydrazone porous covalent organic framework material containing the amino functional group in gaseous iodine adsorption.
According to research, the amino functionalized hydrazone covalent organic framework material has good gaseous iodine adsorption capacity at the adsorption temperature of 75 ℃, and can be used as an adsorption material for effectively adsorbing gaseous iodine.
The invention also provides a gaseous iodine adsorbent which comprises the hydrazone porous covalent organic framework material containing the amino functional group.
Preferably, the gaseous iodine adsorbent further comprises other gaseous iodine adsorbing materials which act synergistically with the hydrazone-based porous covalent organic framework material containing amino functional groups.
In order to meet the use requirements of different scenes, the gaseous iodine adsorbent can preferably further comprise corresponding auxiliary materials.
Compared with the prior art, the invention has the beneficial effects that:
the invention provides a porous hydrazone covalent organic framework material containing amino functional groups, which is prepared by carrying out an acetic acid catalytic reaction on amino functional dihydrazide monomers containing different reactive functional groups and 2,4,6- (4-aldehyde phenyl) -1,3, 5-triazine monomers in an organic solvent under the protection action of inert gas. The preparation method is a new strategy for designing and synthesizing the amino functionalized hydrazone covalent organic framework material, and has the advantages of simplicity, convenience, short reaction period and the like. Meanwhile, the porous hydrazone covalent organic framework material containing the amino functional group contains abundant amino functional sites, has the advantages of good crystallinity, high specific surface area, high stability and the like, can be used as an adsorption material for effectively adsorbing gaseous iodine, and has important popularization and application values.
Drawings
FIG. 1 is a schematic diagram of the synthesis of hydrazone-based porous covalent organic framework materials containing amino functional groups;
FIG. 2 is a powder X-ray diffraction pattern of a hydrazone-based porous covalent organic framework material containing amino functional groups;
FIG. 3 is a Fourier infrared spectrum of a hydrazone-based porous covalent organic framework material containing amino functional groups;
FIG. 4 is a hydrazone-based porous covalent organic framework material containing amino functional groups13C solid nuclear magnetic resonance spectrogram;
FIG. 5 is a thermogravimetric analysis curve of a hydrazone-based porous covalent organic framework material containing an amino functional group under a nitrogen atmosphere;
FIG. 6 is a scanning electron microscope image of hydrazone-based porous covalent organic framework material containing amino functional groups;
FIG. 7 is a graph showing nitrogen desorption curves of hydrazone-based porous covalent organic framework materials containing amino functional groups;
FIG. 8 is a graph showing the adsorption amount of gaseous iodine by a hydrazone-based porous covalent organic framework material having an amino functional group as a function of time;
FIG. 9 is a graph showing the desorption rate of gaseous iodine from a hydrazone-based porous covalent organic framework material having an amino functional group as a function of time.
Detailed Description
The following further describes the embodiments of the present invention. It should be noted that the description of the embodiments is provided to help understanding of the present invention, but the present invention is not limited thereto. In addition, the technical features involved in the embodiments of the present invention described below may be combined with each other as long as they do not conflict with each other.
The experimental procedures in the following examples were carried out by conventional methods unless otherwise specified, and the test materials used in the following examples were commercially available by conventional methods unless otherwise specified.
EXAMPLE 1 preparation of Hydrazone-based porous covalent organic framework materials containing amino functional groups
As shown in the synthesis scheme of fig. 1, the preparation method of the hydrazone porous covalent organic framework material containing an amino functional group in this embodiment specifically includes the following steps:
(1) 2,4,6- (4-aldehyde group)Phenyl) -1,3, 5-triazine (Tz, 7.87mg,0.02mmol), amino-functional dihydrazide monomer (NH)26.3mg of-Th, 0.03mmol) and 1.0mL of a mesitylene/dioxane mixed solvent (the volume ratio of mesitylene to dioxane is 1:1) are placed in a 10mL pressure-resistant reaction bottle, and after the mixture is fully and uniformly mixed, 0.1mL of 6M acetic acid solution is added.
(2) The pressure-resistant reaction bottle is quickly sealed after bubbling for 10min by argon gas, and then the pressure-resistant reaction bottle is placed in an oven at 110 ℃ for reaction for three days.
(3) Cooling to room temperature after the reaction is finished, collecting precipitates through suction filtration, washing the precipitates with tetrahydrofuran and absolute ethyl alcohol for three times in sequence, and finally drying in a vacuum drying oven at 100 ℃ for 24 hours to obtain yellow solid powder, namely hydrazone porous covalent organic framework material containing amino functional groups (NH), namely amino functionalized hydrazone covalent organic framework material (NH)2-Th-Tz COF)。
Experimental example 1 Performance measurement of amino-functionalized hydrazone-based covalent organic framework Material
Hydrazone porous covalent organic framework materials (NH) containing amino functional groups prepared in example 12-Th-Tz COF) is the test material, on which the performance measurements are carried out.
(1) X-ray powder diffraction measurement
NH was measured at room temperature using an X-ray powder diffractometer of the Japanese Science Ultima type IV2-powder X-ray diffraction pattern of Th-Tz COF measured with Cu ka radiation, 2 θ ranging from 2 ° to 40 °, current 40mA and voltage 30 kV.
The measurement results are shown in FIG. 2, in which 2.3 °, 4.8 °, 6.2 ° and 8.1 ° are NH2The characteristic diffraction peak of-Th-Tz COF shows that the crystal property is better.
(2) Fourier Infrared Spectroscopy (FT-IR) determination
NH spectrometer using Spectrum Two FT-IR spectrometer from PerkinElmer, Germany2The KBr pellet (sample to KBr ratio 1:100) of the-Th-Tz COF sample was measured. The measurement results are shown in FIG. 3, wherein a is amino-functionalized dihydrazide monomer, b corresponds to amino-functionalized hydrazone porous covalent organic framework material, and c is 2,4,6- (4-aldehyde benzeneYl) -1,3, 5-triazine. In the Fourier transform Infrared (FT-IR) spectrum of b, 1665cm-1The peak is the characteristic peak of carbonyl group of amino functionalized hydrazone covalent organic framework material and is 1611cm-1The characteristic peak of C-N bond appears, which means that Schiff base reaction occurs between corresponding monomers, and the concentration is 3100-3484 cm-1The broad peak at (a) represents the presence of an amino group in the structure. The characteristic amino group peaks (3333, 3446 cm) in the infrared spectrum of b can be found by comparing with the infrared spectra of a and c-1) And characteristic peak of aldehyde group (1706 cm)-1) The occurrence of (a) is obviously weakened, and further proves that Schiff base condensation reaction occurs between the two monomers.
(3) Solid nuclear magnetic carbon spectrometry
NH pair by adopting BrukeraVANCE III HD 400MHz nuclear magnetic resonance spectrometer2-Th-Tz COF solid nuclear magnetic carbon spectroscopy. The results are shown in fig. 4, in which the peak at 142.99ppm is assigned as C ═ N characteristic peak, indicating that hydrazone bond-linked covalent organic frameworks were successfully prepared by the preparation method of example 1. The peak at 158.29ppm was assigned to the carbon atom attached to the amino functional group, the peak at 166.15ppm was assigned to the characteristic peak of the carbon atom on the carbonyl group, and the peaks at 133.74, 125.02 and 116.67 ppm were assigned to the characteristic peaks of the carbon atoms on the other benzene rings.
(4) Thermogravimetric analysis
NH was measured under nitrogen atmosphere using a German relaxation-resistant TG209F3 thermogravimetric analyzer2Thermogravimetric analysis (TGA) was carried out on-Th-Tz COF at a temperature ranging from 30 to 800 ℃ and at a rate of temperature rise of 10 ℃/min. As shown in figure 5, it can be observed from the TGA curve that mass is lost only 7.2% at temperatures less than 316 ℃, which may be caused by the presence of small amounts of solvent guest molecules in the channels, while at temperatures above 316 ℃, the TGA curve of the material drops sharply, due to decomposition of the material. The above results illustrate NH2the-Th-Tz COF is stable to 316 ℃ in a nitrogen atmosphere.
(5) Observation by scanning electron microscope
NH pair Using Gemini 500 scanning Electron microscope from Zeiss, Germany2the-Th-Tz COF is observed by a scanning electron microscope, and the observation result is shown in the figureShown in FIG. 6, shows NH2the-Th-Tz COF is a porous nanorod morphology.
(6) Characterization of nitrogen adsorption and desorption
The American Mike ASAP 2020 vs. NH was used2-Th-Tz COF Nitrogen adsorption-desorption experiments to evaluate NH2Porosity of the-Th-Tz COF. Before testing, tetrahydrofuran was used for the reaction on NH2-Th-Tz COF was treated with solvent exchange for 24h and then activated with heat at 120 ℃ under dynamic vacuum overnight. FIG. 7 is NH2Adsorption and desorption isotherms of-Th-Tz COF, indicating that it is a typical porous material. At the same time, NH is calculated2BET specific surface area (S) of-Th-Tz COFBET) Is 509.7 m2g-1. Furthermore, NH was calculated from the pore size distribution data (inset in FIG. 7) by the non-localized density functional theory2The pore size of the-Th-Tz COF is mainly centered at 2.87 nm.
(7) Gas iodine adsorption and desorption experiment
Accurately weighing 5mgNH2the-Th-Tz COF is placed in a 2mL open glass bottle, then the glass bottle is placed in a 20mL glass bottle containing 50mg of iodine, and the glass bottle is sealed and then placed in a constant temperature oven at 75 ℃. At specific time points (0, 800, 1600, 2400, 3200, 4000, 4800min) the vials were removed, quickly weighed and data recorded, and then quickly replaced into the larger vial, again placed in the oven until the mass of the vial no longer increased. The test results are shown in FIG. 8, NH2the-Th-Tz COF showed a very fast adsorption rate in the first 10 hours and reached a maximum adsorption of 1.86g/g at 45 hours. The vials that no longer increased in mass were removed, placed open in an oven at 135 ℃ and removed at specific time points (0, 200, 400, 600, 800, 1000, 1200, 1400min), quickly weighed and data recorded, and quickly returned to the oven until the vial no longer decreased in mass. The test results are shown in FIG. 9, NH2The desorption of-Th-Tz COF reached a maximum desorption of 95.7% at 12 hours. The above results show that NH2the-Th-Tz COF has good gaseous iodine adsorption capacity and can be used for gaseous iodine adsorption.
The embodiments of the present invention have been described in detail, but the present invention is not limited to the described embodiments. It will be apparent to those skilled in the art that various changes, modifications, substitutions and alterations can be made in these embodiments without departing from the principles and spirit of the invention, and the scope of protection is still within the scope of the invention.

Claims (10)

1. The hydrazone porous covalent organic framework material containing the amino functional group is characterized by having a structure shown as a formula (I):
Figure FDA0003360710060000011
2. the method for preparing the hydrazone porous covalent organic framework material with the amino functional group, as claimed in claim 1, is characterized in that the hydrazone porous covalent organic framework material with the amino functional group is prepared by performing an acetic acid catalytic reaction on an amino functional dihydrazide monomer shown as a formula (II) and 2,4,6- (4-aldehyde phenyl) -1,3, 5-triazine in an organic solvent under the protection of inert gas atmosphere:
Figure FDA0003360710060000012
3. the method of claim 2, wherein the molar ratio of the 2,4,6- (4-formylphenyl) -1,3, 5-triazine to the amino-functionalized dihydrazide monomer is 1: (1-1.5).
4. The method for preparing the amino functional group-containing hydrazone-based porous covalent organic framework material according to claim 2, wherein the molar amount of acetic acid used for the acetic acid catalytic reaction is 1-10 times that of the amino functional dihydrazide monomer.
5. The method for preparing the hydrazone-based porous covalent organic framework material having an amino functional group according to claim 2, wherein the temperature of the acetic acid-catalyzed reaction is 90 to 120 ℃ and the time is 3 to 5 days.
6. The method of claim 2, wherein the organic solvent comprises a mixed solvent of mesitylene and dioxane and a mixed solvent of mesitylene and N, N' -dimethylformamide.
7. The method of claim 6, wherein the organic solvent is a mixed solvent of mesitylene and dioxane, and the volume ratio of mesitylene to dioxane is 1: 1-9.
8. Use of the amino functional group-containing hydrazone-based porous covalent organic framework material of claim 1 in gaseous iodine adsorption.
9. A gaseous iodine adsorbent comprising the amino functional group-containing hydrazone-based porous covalent organic framework material of claim 1.
10. The gaseous iodine adsorbent of claim 9, further comprising other gaseous iodine adsorbing material cooperating with said porous covalent organic framework material of hydrazone with amino functional group.
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CN114957577A (en) * 2022-05-20 2022-08-30 华南师范大学 Porous hydrazone covalent organic framework material with flexible framework and preparation method and application thereof
CN115057981A (en) * 2022-08-18 2022-09-16 北京市疾病预防控制中心 Amino-functionalized covalent organic framework material and preparation method and application thereof

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Publication number Priority date Publication date Assignee Title
CN114957577A (en) * 2022-05-20 2022-08-30 华南师范大学 Porous hydrazone covalent organic framework material with flexible framework and preparation method and application thereof
CN114957577B (en) * 2022-05-20 2023-09-29 华南师范大学 Porous hydrazone covalent organic framework material with flexible framework, and preparation method and application thereof
CN115057981A (en) * 2022-08-18 2022-09-16 北京市疾病预防控制中心 Amino-functionalized covalent organic framework material and preparation method and application thereof

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