Synthetic method and application of efficient iodine adsorption material

Abstract

The invention belongs to the technical field of iodine adsorption materials, and discloses a synthetic method and application of a high-efficiency iodine adsorption material, the synthetic method comprises the following steps: S1, adding an organic aldehyde ligand into a container, adding a solvent, and stirring to completely dissolve the aldehyde ligand; s2, slowly dropwise adding the solution into an organic amine ligand solution, and completely mixing the organic amine ligand solution with an amino ligand; s3, sealing the mixed solution, and stirring at room temperature until the color becomes dark; s4, after the reaction is completed, distributing reaction liquid into a small glass bottle, tightening a bottle cap, unscrewing a half circle, and placing the small glass bottle in a protective atmosphere; after the gas liquid diffuses for several days, macroscopic crystals are formed at the bottom of the small glass bottle. The adsorption material obtained through synthesis is applied to volatile and radioactive iodine. The crystalline adsorption material synthesized by the method is good in stability, high in iodine adsorption efficiency and high in adsorption rate, and can be used for nuclear waste treatment and radioactive iodine capture.

Description

Technical Field

[0001] The present invention relates to the technical field of iodine adsorption materials, and in particular to a synthesis method and application of a high-efficiency iodine adsorption material. Background Art

[0002] Nuclear energy is one of the most promising clean energy sources for the future of mankind. However, the limitations of spent nuclear fuel reprocessing and improper handling of radioactive nuclide wastes have hindered the further sustainable development of nuclear energy. Among them, volatile and radioactive iodine isotopes (such as 129 I and 131 I) has caused great environmental and safety concerns due to its dangerous effects of radioactivity, chemical and biological toxicity.

[0003] Porous covalent cages (PCCs) are cage-type organic molecules with a three-dimensional structure formed by covalent bonds of light elements such as C, H, O, N, and B. This type of material has broad application prospects in adsorption separation, energy storage, sensing, catalysis, and pollutant capture due to its rigid skeleton structure, durable shape, adjustable pore structure, large specific surface area, good thermal / chemical stability, and easy post-modification. For example, metal organic frameworks (MOFs), covalent organic frameworks (COFs), and porous organic polymers (POPs) can effectively capture iodine, but it is still extremely challenging to directly visualize the interaction of iodine capture materials. Summary of the Invention

[0004] The present invention aims to provide a method for synthesizing and applying a highly efficient iodine adsorption material, thereby obtaining a crystalline adsorption material with good stability, high iodine adsorption efficiency, and rapid adsorption rate. This material can be used for nuclear waste treatment, radioactive iodine capture, and other applications. This solves the problems encountered in the prior art.

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

[0006] A method for synthesizing a high-efficiency iodine adsorption material, characterized by comprising the following steps:

[0007] S1. Add an organic aldehyde ligand into a container, add a solvent and stir to completely dissolve the aldehyde ligand;

[0008] S2. Slowly add the solution prepared in S1 dropwise to the organic amine ligand solution and stir to completely mix it with the amino ligand;

[0009] S3. Seal the mixed solution prepared in S2 and stir at room temperature until the color becomes darker;

[0010] S4. After the reaction of the solution in S3 is completed, the reaction solution is divided into a glass vial, the cap is tightly closed and then loosened half a turn, and the vial is placed in a protective atmosphere for gas-liquid diffusion. Crystals visible to the naked eye form at the bottom of the glass vial, indicating that the iodine adsorption material is synthesized.

[0011] Furthermore, in S1, the aldehyde ligand is a bidentate, tridentate, tetradentate or other dentate organic compound based on an aromatic or aliphatic parent nucleus, and such aldehyde ligand has a planar structure or a three-dimensional structure.

[0012] Furthermore, in S2, the amino ligand is a bidentate, tridentate, tetradentate or other dentate organic compound based on an aliphatic or aromatic parent nucleus; and such amino ligand has a planar structure or a three-dimensional structure.

[0013] Furthermore, in S2, the amount ratio of the aldehyde ligand to the amino ligand is 0.8-1.5:1.

[0014] Furthermore, in S1, the solvent is a polar organic solvent.

[0015] Furthermore, in S2, the solvent of the amino ligand is a polar organic solvent, and the dripping time is 5 minutes.

[0016] Furthermore, in S3 , the sealed mixed solution is stirred at 298 K for 8 hours.

[0017] Furthermore, in S4, the same volume of halogenated aromatic hydrocarbon and acetonitrile were added to the glass vial containing the reaction solution, and gas-liquid diffusion was carried out in an acetonitrile atmosphere for 15 days. The synthesized crystals were yellow-green regular blocks.

[0018] Furthermore, in S1, the solvent is a low-polarity organic solvent.

[0019] Furthermore, in S2, the solvent of the amino ligand solution is a low-polarity organic solvent, and the dripping time is 10 minutes.

[0020] Furthermore, in S3 , the sealed mixed solution was stirred at 298 K for 3 hours, and the color of the mixed solution changed from orange-yellow to fluorescent green and the solution became turbid.

[0021] Furthermore, in S4, the glass vial containing the reaction solution was subjected to gas-liquid diffusion in an ether atmosphere for 3 days, and the synthesized crystals were in the form of yellow-green clusters.

[0022] The adsorption material synthesized by the above-mentioned method for synthesizing a high-efficiency iodine adsorption material is used in the application of volatile and radioactive iodine. The adsorption of iodine ions or iodine molecules by the adsorption material includes physical adsorption and chemical adsorption; iodine ions form multiple effective hydrogen bonds and other weak forces near the skeleton of the adsorption material.

[0023] The beneficial effects of the technical solution are:

[0024] 1. The synthesized adsorption material has a rich pore structure and a large specific surface area, which provides more active sites for the adsorption of iodine molecules; the functional groups such as amino and aldehyde groups in the adsorption material can form stable interactions with iodine molecules, and the iodine adsorption efficiency and capacity are high.

[0025] 2. The solvents used in the synthesis process can be recycled and reused during the preparation process, reducing environmental pollution and waste. Moreover, the preparation process is simple and easy to operate, without the use of harmful catalysts or additives, which is in line with the concept of green chemistry.

[0026] 3. During the synthesis process, the reaction is uniform, and the product has good crystallinity and stability. Moreover, bulk crystallization is slowly obtained in a protective atmosphere through the gas-liquid diffusion method, which makes the material's structural stability and adsorption performance strong.

[0027] 4. The adsorption of iodine (ions or molecules) by the synthesized adsorption material is both physical adsorption and chemical adsorption. Among them, the iodine adsorbed on the material is in the form of polyiodide ions (I3 - 、I5 - or I7 - ) exists near the material's skeleton, forming multiple effective hydrogen bonds and other weak interactions. Iodine species adsorbed onto the material were directly observed using X-ray single crystal diffraction. The adsorption rate is rapid, typically reaching saturation within 10 minutes, and the adsorption capacity is high, typically ranging from 4-6 g / g, with a maximum exceeding 7 g / g. This makes it suitable for treating iodine-containing wastewater, exhaust gas, and other environmental pollution issues, possessing significant application value. Furthermore, the material can be used in nuclear waste treatment and radioactive iodine capture, providing strong support for nuclear safety and environmental protection. BRIEF DESCRIPTION OF THE DRAWINGS

[0028] Figure 1 This is a crystal diagram of the adsorption material synthesized in Example 1 of the present invention;

[0029] Figure 2 is the chemical reaction equation for synthesizing the adsorption material in Example 1 of the present invention;

[0030] Figure 3 This is a crystal diagram of the adsorption material synthesized in Example 2 of the present invention. DETAILED DESCRIPTION

[0031] The present invention will be further described in detail below with reference to the accompanying drawings and embodiments:

[0032] Example 1

[0033] 118 mg (0.20 mmol) of organic aldehyde ligand (aldehyde ligand is a bidentate organic compound based on aromaticity) was added to a 100 mL round-bottom flask, followed by the addition of 30 mL of CHCl3 and stirring until completely dissolved; 38 mg (0.26 mmol) of tris(2-aminoethyl)amine (TREN) solution dissolved in 10 mL of CHCl3 was slowly added dropwise (about 5 minutes) to the stirred mixture; the mixture was then sealed and stirred at room temperature (298 K) for 8 hours until the color changed from orange-yellow to fluorescent green; after the reaction was completed, the reaction solution was evenly divided into 40 5 mL glass vials, and 1 mL of chlorobenzene and 1 mL of acetonitrile were added to each vial; after mixing 3 mL of the solution, the bottle cap was tightly closed and then loosened half a turn, and placed in an acetonitrile atmosphere for gas-liquid diffusion for 15 days, and finally yellow-green regular block crystals were formed at the bottom of the bottle, which was the desired adsorbent material. The crystal structure of the synthesized adsorbent material is shown in the figure below. Figure 1 The chemical formula for synthesizing the adsorption material is shown in Figure 2 shown.

[0034] Example 2

[0035] 353 mg (0.60 mmol) of organic aldehyde ligand (aldehyde ligand is a tridentate organic compound based on an aliphatic mother nucleus) was added to a 250 mL round-bottom flask, and then 100 mL of CH2Cl2 was added and stirred until dissolved; 114 mg (0.78 mmol) of tris(2-aminoethyl)amine (TREN) solution dissolved in 20 mL of CH2Cl2 was slowly added dropwise (about 10 minutes) to the stirred mixture; the mixture was then sealed and stirred at room temperature (298 K) for 3 hours until the color changed from orange-yellow to fluorescent green and the solution became turbid; after the reaction was completed, the reaction solution was evenly divided into 60 5 mL glass vials, the vials were tightly capped and loosened half a turn, and placed in an ether atmosphere for gas-liquid diffusion for 3 days, and a large number of yellow-green clustered crystals were formed at the bottom of the vial, which was the desired adsorbent material. The crystal diagram of the synthesized adsorbent material is shown in FIG. Figure 3 shown.

[0036] Example 3

[0037] Place the adsorption material crystals in an environment of 101.325KPa and 273-373K and add iodine vapor. After a period of time, the adsorption reaches saturation and the color of the crystals can be observed to turn into opaque black.

[0038] The above is only an embodiment of the present invention, and common knowledge such as the specific technical solutions or characteristics in the solution is not described in detail here. It should be pointed out that for those skilled in the art, without departing from the technical solution of the present invention, several variations and improvements can be made, which should also be regarded as the scope of protection of the present invention, and these will not affect the effect of the implementation of the present invention and the practicality of the patent. The scope of protection required by this application shall be based on the content of its claims, and the specific implementation methods and other records in the description can be used to interpret the content of the claims.

Claims

1. A method for synthesizing a high-efficiency iodine adsorption material, characterized in that: The following steps are involved: S1. Add an organic aldehyde ligand into a container, add a solvent and stir to completely dissolve the aldehyde ligand; S2. Slowly add the solution prepared in S1 dropwise to the organic amine ligand solution and stir to completely mix it with the amino ligand; S3. Seal the mixed solution prepared in S2 and stir at room temperature until the color becomes darker; S4. After the reaction of the solution in S3 is completed, the reaction liquid is divided into a glass vial, the bottle cap is tightly closed and then loosened half a turn, and placed in a protective atmosphere. After the gas and liquid diffuse for several days, visible crystals are formed at the bottom of the glass vial, and the iodine adsorption material is synthesized.

2. The method for synthesizing a high-efficiency iodine adsorption material according to claim 1, wherein: In S1, the aldehyde ligand is a bidentate, tridentate, tetradentate or other dentate organic compound based on an aromatic or aliphatic parent nucleus, and such aldehyde ligand has a planar structure or a three-dimensional structure.

3. The method for synthesizing a high-efficiency iodine adsorption material according to claim 2, wherein: In S2, the amino ligand is a bidentate, tridentate, tetradentate or other dentate organic compound based on an aliphatic or aromatic parent nucleus, and such amino ligand has a planar structure or a three-dimensional structure.

4. The method for synthesizing a high-efficiency iodine adsorption material according to claim 3, characterized in that: In S2, the molar ratio of the aldehyde ligand to the amino ligand is 0.8-1.5:

1.

5. The method for synthesizing a high-efficiency iodine adsorption material according to claim 4, characterized in that: In S1, the solvent is a polar organic solvent.

6. The method for synthesizing a high-efficiency iodine adsorption material according to claim 5, characterized in that: In S2, the solvent of the amino ligand is a polar organic solvent, and the dropwise addition time is 5 minutes.

7. The method for synthesizing a high-efficiency iodine adsorption material according to claim 6, characterized in that: In S3, the sealed mixed solution was stirred at 298 K for 8 h.

8. The method for synthesizing a high-efficiency iodine adsorption material according to claim 7, characterized in that: In S4, equal volumes of halogenated aromatic hydrocarbon and acetonitrile were added to a glass vial containing the reaction solution, and gas-liquid diffusion was carried out in an acetonitrile atmosphere for 15 days. The synthesized crystals were yellow-green regular blocks.

9. The method for synthesizing a high-efficiency iodine adsorption material according to claim 4, characterized in that: In S1, the solvent is a low-polarity organic solvent.

10. The method for synthesizing a high-efficiency iodine adsorption material according to claim 9, characterized in that: In S2, the solvent of the amino ligand solution is a low-polarity organic solvent, and the dropwise addition time is 10 minutes.

11. The method for synthesizing a high-efficiency iodine adsorption material according to claim 10, characterized in that: In S3, the sealed mixed solution was stirred at 298 K for 3 h, and the color of the mixed solution changed from orange-yellow to fluorescent green and the solution became turbid.

12. The method for synthesizing a high-efficiency iodine adsorption material according to claim 11, characterized in that: In S4, the glass vial containing the reaction solution was subjected to gas-liquid diffusion in an ether atmosphere for 3 days, and the synthesized crystals were in the form of yellow-green clusters.

13. Use of the adsorbent material synthesized by the method for synthesizing a high-efficiency iodine adsorbent according to any one of claims 1 to 12 in volatile and radioactive iodine, characterized in that: The adsorption of iodine ions or iodine molecules by the adsorption material includes physical adsorption and chemical adsorption; iodine ions form a variety of effective hydrogen bonds and other weak forces near the skeleton of the adsorption material.

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