Triazolamine macrocyclic adsorbent material, synthesis method and application thereof
By synthesizing trigonal amine macrocyclic adsorbent materials and utilizing their unique molecular structure and non-covalent interaction with iodine, the problem of insufficient adsorption capacity and kinetics of existing porous materials in radioactive iodine treatment was solved, achieving efficient and stable iodine adsorption effect.
Patent Information
- Authority / Receiving Office
- CN · China
- Patent Type
- Patents(China)
- Current Assignee / Owner
- Filing Date
- 2025-12-25
- Publication Date
- 2026-03-24
AI Technical Summary
Existing porous materials have limitations in adsorption capacity, slow adsorption kinetics, and insufficient stability when dealing with radioactive iodine generated from nuclear facilities, and are also costly.
Using triangular amine macrocyclic adsorbents, a macrocyclic structure with a nitrogen-rich, sulfur-rich heteroatom molecular skeleton was synthesized by using cyclohexanediamine and benzothiadiazole as building blocks. The unique cavity and non-covalent interaction between the macrocyclic structure and iodine functional groups were utilized to achieve efficient adsorption and rapid release.
Triangular amine macrocyclic adsorbents exhibit high iodine adsorption capacity, rapid adsorption kinetics, and excellent cycle stability, making them suitable as efficient and durable adsorbents for nuclear waste treatment, especially for the capture and desorption of radioactive iodine in gas and aqueous environments.
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Figure CN121405720B_ABST
Abstract
Description
Technical Field
[0001] This invention relates to the field of adsorption materials technology, specifically a triangular amine macrocyclic adsorption material, its synthesis method, and its application. Background Technology
[0002] Nuclear energy, as a highly efficient and green clean energy source, plays an indispensable role in addressing global energy demand growth and achieving carbon neutrality. However, radioactive nuclides generated during the operation of nuclear facilities and the disposal of nuclear waste, especially highly volatile and biotoxic radioactive iodine isotopes (such as...), are also a concern. 129 I and 131 (I) poses a serious threat to the ecological environment and public health. 129 I has an extremely long half-life and can cause persistent environmental pollution; although 131 Radioactive iodine (I) has a short half-life but high radioactivity, making it prone to accumulation through the food chain and damaging the human thyroid gland. Therefore, developing novel adsorbent materials capable of efficiently and rapidly capturing radioactive iodine from both gas-liquid and liquid-phase environments is an urgent and important research task in the field of nuclear safety.
[0003] In existing technologies, porous materials such as zeolites and activated carbon have been used to treat iodine pollution, but they have limited adsorption capacity and slow adsorption kinetics. In recent years, various advanced porous materials, such as metal-organic frameworks (MOFs) and covalent organic frameworks (COFs), have shown superior iodine adsorption performance compared to the aforementioned traditional materials due to their high specific surface area and tunable pore structure. However, these porous materials often face stringent environmental limitations, insufficient material stability, and high application costs in practical applications.
[0004] Against this backdrop, macrocyclic molecules with well-defined adsorption sites have attracted significant attention in the field of iodine pollution control due to their unique customizable synthesis and excellent adsorption performance. Unlike traditional porous materials that primarily rely on specific surface area and physisorption, the cavities of macrocyclic molecules provide a unique hydrophobic microenvironment. Through the cavity confinement effect and various non-covalent interactions between iodine and customized functional groups within the cavity, highly efficient adsorption of iodine molecules and ions can be achieved. For example, some electron-rich macrocyclic compounds have shown significant iodine adsorption potential by forming charge-transfer complexes with iodine within their cavities, confirming the feasibility of this strategy. However, existing macrocyclic adsorbent materials still require further improvement in terms of adsorption capacity, adsorption rate, and cycling stability. Summary of the Invention
[0005] The purpose of this invention is to provide a triangular amine macrocyclic adsorbent material to solve the problems mentioned in the background art.
[0006] To achieve the above objectives, the present invention provides the following technical solution:
[0007] A triangular amine macrocyclic adsorbent material, the general structural formula of which is either Formula I or Formula II:
[0008] ; ;
[0009] In the formula, It is any one of the following groups:
[0010] .
[0011] Furthermore, the structural formula of the triangular amine macrocyclic adsorbent material is any one of the following formulas:
[0012] ; .
[0013] Another object of the present invention is to provide a method for synthesizing the above-mentioned triangular amine macrocyclic adsorbent material, comprising the following steps:
[0014] Compound A, 4-formylphenylboronic acid, palladium catalyst and sodium carbonate were mixed and a first solvent was added as the reaction system to obtain a mixture;
[0015] The mixture was refluxed to produce a precipitate, which was then purified to obtain intermediate B.
[0016] Intermediate B and 1,2-cyclohexanediamine were dissolved in a second solvent and refluxed. After the reaction was completed, the mixture was purified to obtain the triangular amine macrocyclic adsorbent material shown in Formula I.
[0017] The general structural formula of compound A is as follows: The general structural formula of the intermediate B is as follows: In the formula, The definition is as described above.
[0018] Furthermore, the synthesis method of the above-mentioned triangular amine macrocyclic adsorbent material also includes the following steps:
[0019] The triangular amine macrocyclic adsorbent material shown in Formula I was dissolved in a third solvent, and sodium borohydride was added under ice bath for reflux reaction. After the reaction was completed, the material was purified to obtain the triangular amine macrocyclic adsorbent material shown in Formula II.
[0020] Furthermore, the palladium catalyst is tetra(triphenylphosphine)palladium.
[0021] Furthermore, the first solvent is a mixture of toluene, ethanol and water.
[0022] Furthermore, the second solvent is a mixture of chloroform and methanol.
[0023] Furthermore, the third solvent is a mixture of chloroform and methanol.
[0024] Another object of the present invention is to provide an application of the above-mentioned triangular amine macrocyclic adsorbent material in iodine adsorption.
[0025] Another object of the present invention is to provide an application of the above-mentioned triangular amine macrocyclic adsorbent material in nuclear waste treatment.
[0026] This invention provides a triangular amine macrocyclic adsorbent with a simple synthesis route, mild reaction conditions, easy operation, and easy large-scale preparation. This triangular amine macrocyclic adsorbent exhibits high efficiency in iodine adsorption in practical applications, and also possesses excellent cycle stability, enabling repeated use through simple processing. It achieves iodine capture and desorption, improving environmental adaptability and cycle life, providing a research foundation for its practical application as a high-efficiency and durable adsorbent in nuclear waste treatment, especially demonstrating comprehensive performance advantages in radioactive iodine adsorption. This invention showcases the structural advantages of triangular amine macrocycles as iodine adsorbents, providing a feasible material design concept and technical basis for developing a new generation of multi-environmentally adaptable radioactive iodine adsorbents. Attached Figure Description
[0027] Figure 1 The synthesis route diagram of the triangular amine macrocyclic adsorbent material provided in the embodiments of the present invention is shown.
[0028] Figure 2 The image shows the hydrogen NMR spectrum of BDT (400 MHz, CDCl3, 298 K).
[0029] Figure 3 The image shows the carbon NMR spectrum of BDT (400 MHz, CDCl3, 298 K).
[0030] Figure 4 The 1H NMR spectrum of TA-1 (400 MHz, CDCl3, 298 K).
[0031] Figure 5 The carbon NMR spectrum of TA-1 (400 MHz, CDCl3, 298 K).
[0032] Figure 6 The 1H NMR spectrum of TA-2 (400 MHz, CDCl3, 298 K).
[0033] Figure 7 This is a schematic diagram of the crystal structure of TA-1.
[0034] Figure 8 The nitrogen adsorption isotherms are for TA-1(a) and TA-2(b).
[0035] Figure 9 Thermogravimetric analysis curves for TA-1(a) and TA-2(b).
[0036] Figure 10 The graphs show the changes in iodine vapor adsorption capacity of TA-1(a) and TA-2(b) over time, with the inset showing the morphological changes of the materials during the iodine vapor adsorption process.
[0037] Figure 11 The figure shows the adsorption kinetics curves of iodine adsorption in water by the trigonal amine macrocyclic adsorbent material; in the figure, (a) shows the adsorption of I3 by TA-1 (4 mg). - (a) Adsorption kinetics curves of aqueous solution ([KI] / [I2], 0.15 mM, 4 mL); (b) Adsorption kinetics curves of I3 by TA-1. - (c) shows the pseudo-second-order kinetic model diagram; (d) shows the adsorption of I3 by TA-2 (2 mg). - Adsorption kinetics curves of aqueous solution ([KI] / [I2], 0.15 mM, 4 mL); (d) adsorption of I3 by TA-2. - The quasi-second-order dynamic model diagram. Detailed Implementation
[0038] The technical solutions of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative effort are within the scope of protection of the present invention.
[0039] In one embodiment of the present invention, a triangular amine macrocyclic adsorbent material is provided, the general structural formula of which is either Formula I or Formula II:
[0040] ; ;
[0041] In the formula, It is any one of the following groups:
[0042] .
[0043] Preferably, the structural formula of the triangular amine macrocyclic adsorbent material is any one of the following formulas:
[0044] ; .
[0045] like Figure 1 As shown, in another embodiment of the present invention, a method for synthesizing the above-mentioned triangular amine macrocyclic adsorbent material is also provided, comprising the following steps:
[0046] S1. Compound A, 4-formylphenylboronic acid, palladium catalyst and sodium carbonate are mixed and the first solvent is added as the reaction system to obtain a mixture;
[0047] S2. The mixture is refluxed to produce a precipitate, which is then purified to obtain intermediate B.
[0048] S3. Dissolve intermediate B and 1,2-cyclohexanediamine in a second solvent and reflux the reaction. After the reaction is completed, the mixture is purified to obtain the triangular amine macrocyclic adsorbent material shown in Formula I.
[0049] S4. Dissolve the triangular amine macrocyclic adsorbent material shown in Formula I in a third solvent, add sodium borohydride under ice bath and reflux reaction. After the reaction is completed, purify to obtain the triangular amine macrocyclic adsorbent material shown in Formula II.
[0050] The general structural formula of compound A is as follows: Preferably, it is 4,7-dibromo-2,1,3-benzothiadiazole; the general structural formula of intermediate B is... .
[0051] Preferably, the palladium catalyst is tetra(triphenylphosphine)palladium; the first solvent is a mixed solvent of toluene, ethanol and water; the second solvent is a mixed solvent of chloroform and methanol; and the third solvent is a mixed solvent of chloroform and methanol.
[0052] This invention presents a series of triangular amine macrocyclic molecules with benzothiadiazole as adsorption sites, designed and synthesized based on efficient imine condensation reactions, serving as iodine adsorbents. The cyclohexanediamine unit provides nitrogen atoms, while the benzothiadiazole unit provides both nitrogen and sulfur atoms as potential iodine adsorption sites. Furthermore, the closed-loop ring structure is expected to enhance iodine capture capacity. These macrocyclic molecules combine the advantages of customized synthesis, strong host-guest binding, and excellent adsorption-desorption properties. Moreover, from the perspective of adsorption mechanism research, their unique heteroatom-rich characteristics demonstrate high iodine adsorption capacity, rapid adsorption kinetics, and excellent cycling stability.
[0053] Example 1: This example provides a method for synthesizing an intermediate (denoted as BDT), as follows:
[0054] In a 500 mL round-bottom flask, 4,7-dibromo-2,1,3-benzothiadiazole (7.84 g, 26.67 mmol), 4-formylphenylboronic acid (10 g, 66.70 mmol), tetrakis(triphenylphosphine)palladium (300 mg, 0.27 mmol), and sodium carbonate (18.4 g, 133.40 mmol) were added, along with a mixed solvent of toluene (200 mL), ethanol (100 mL), and water (25 mL). The resulting mixture was refluxed at 80 °C under a nitrogen atmosphere for 16 hours. After the reaction, the filter cake was collected and purified by silica gel column chromatography to obtain a yellow solid product, which was the intermediate BDT (6.2 g, 67%). The 1H NMR spectrum and 1C NMR spectrum of the intermediate BDT are shown below. Figure 2 and Figure 3 As shown.
[0055] Example 2: This example provides a method for synthesizing a triangular amine macrocyclic adsorbent (denoted as TA-1), as detailed below:
[0056] In a 500 mL round-bottom flask, 1,2-cyclohexanediamine (33.2 mg, 0.29 mmol) and BDT (100 mg, 0.29 mmol) synthesized in Example 1 were dissolved in a mixed solvent of chloroform (50 mL) and methanol (100 mL). The reaction system was refluxed at 70 °C for 6 hours. After the reaction was completed, the filter cake was collected and purified by recrystallization with chloroform and acetonitrile to finally obtain the triangular amine macrocyclic adsorbent TA-1 (92.1 mg, 75%). The 1H NMR spectrum and 1C NMR spectrum of the triangular amine macrocyclic adsorbent TA-1 are shown below. Figure 4 and Figure 5 As shown, its crystal structure is as follows Figure 7 As shown. Additionally, the nitrogen adsorption isotherm of the triangular amine macrocyclic adsorbent TA-1 is shown below. Figure 8 As shown in (a), its thermogravimetric analysis curve is as follows: Figure 9 As shown in (a).
[0057] Example 3: This example provides another method for synthesizing a triangular amine macrocyclic adsorbent (denoted as TA-2), as follows:
[0058] In a 250 mL round-bottom flask, TA-1 (100 mg, 0.079 mmol) synthesized in Example 2 was dissolved in a mixed solvent of chloroform (60 mL) and methanol (60 mL). The mixture was then cooled in an ice-water bath, followed by the slow addition of sodium borohydride (35.8 mg, 0.95 mmol), and the mixture was refluxed at 70 °C for 16 hours. After the reaction was complete, the mixture was extracted with dichloromethane and water, and the organic phase was collected. The solvent was removed under reduced pressure to obtain a yellow solid product, which was the triangular amine macrocyclic adsorbent TA-2 (100.9 mg, 86%). The 1H NMR spectrum of the triangular amine macrocyclic adsorbent TA-2 is shown below. Figure 6 As shown. Additionally, the nitrogen adsorption isotherm of the triangular amine macrocyclic adsorbent TA-2 is shown below. Figure 8 As shown in (b), its thermogravimetric analysis curve is as follows: Figure 9 As shown in (b).
[0059] Example 4: The triangular amine macrocyclic adsorbents TA-1 and TA-2 synthesized in Examples 3 and 4 above were tested for iodine vapor adsorption performance, as detailed below:
[0060] 10 mg of the trigonal amine macrocyclic adsorbent TA-1 or TA-2 was placed in an open, pre-weighed 2 mL sample vial. This vial was then transferred to a sealed 20 mL glass vial containing 1 g of solid iodine. The entire apparatus was heated in an oven at 75 °C under normal pressure and maintained at a constant temperature. During adsorption, the sample vial was weighed at regular intervals. After each weighing, the sample vial was returned to the system to continue adsorbing iodine vapor until the sample mass remained constant, indicating that adsorption had reached equilibrium. The test results are as follows: Figure 10 As shown, under normal pressure of 353 K, the adsorption capacity of the triangular amine macrocyclic adsorbent gradually increases with time, and finally the maximum adsorption capacity of TA-1 reaches 3.87 g·g at adsorption equilibrium after 24 h. -1 , specifically Figure 10 As shown in (a); while TA-2 reaches a higher maximum adsorption capacity of 4.75 g·g at 22 h adsorption equilibrium. -1 , specifically Figure 10 As shown in (b), the experimental results show that both the triangular amine macrocyclic adsorbents TA-1 and TA-2 have strong iodine adsorption capacity, with TA-2 exhibiting a stronger iodine adsorption capacity than TA-1.
[0061] Example 5: The adsorption kinetics of the triangular amine macrocyclic adsorbents TA-1 and TA-2 synthesized in Examples 3 and 4 above were tested in water for iodine adsorption, as detailed below:
[0062] Add 4 mL of 0.15 mM I3 to a 5 mL glass bottle. -An aqueous solution ([KI] / [I2]) was prepared, followed by the addition of 4 mg TA-1 or 2 mg TA-2 as adsorbents. The mixture was stirred at room temperature, and the UV-Vis spectra of the supernatant were measured at regular time intervals. The absorbance values at 288 nm and 350 nm were recorded. Adsorption kinetics were calculated and fitted based on the change in absorbance at 285 nm. Figure 11 As shown in (a) and (c). Calculations were performed using a pseudo-second-order kinetic fitting model of the triangular amine macrocyclic adsorbents TA-1 and TA-2, as follows... Figure 11 As shown in (b) and (d), the adsorption rate of TA-1 is 7.34 × 10⁻⁶. -3 g·mg -1 ·min -1 The adsorption rate of TA-2 is 1.61 × 10⁻⁶. -2 g·mg -1 ·min -1 .
[0063] In the iodine vapor adsorption test, the triangular amine macrocyclic adsorbent synthesized in this embodiment of the invention exhibited ultra-high capacity, especially TA-2 after reduction with sodium borohydride, which had an equilibrium adsorption capacity as high as 4.75 g·g⁻¹. -1 It significantly surpasses its precursor TA-1 (3.87 g·g⁻¹). -1 Furthermore, TA-2 reacts with I3 in water. - The adsorption rate reached 1.61 × 10⁻⁶. -2 g·mg -1 ·min -1 The adsorption rate is more than twice that of TA-1, achieving rapid adsorption of iodine. Furthermore, this triangular amine macrocyclic adsorbent exhibits excellent cycling stability and can be reused with simple processing, providing a research foundation for its practical application as a highly efficient and durable adsorbent in nuclear waste treatment.
[0064] In summary, this invention utilizes cyclohexanediamine and benzothiadiazole as building blocks to construct a molecular structure with a nitrogen-rich, sulfur-rich heteroatom molecular framework and a large ring cavity. The reduced triangular amine macrocyclic adsorbent TA-2 exhibits stronger iodine adsorption performance due to changes in the electronic state of nitrogen atoms and the introduction of hydrogen bonds. The synthesis of this triangular amine macrocyclic adsorbent is simple, the reaction conditions are mild, and it is easy to prepare in large quantities. Utilizing the multiple non-covalent interactions between this triangular amine macrocyclic adsorbent and iodine, high-capacity, rapid adsorption and reversible release of radioactive iodine are achieved in both gas and aqueous phases. This provides a novel adsorbent material for the efficient capture of iodine from nuclear waste, enabling efficient adsorption of iodine from nuclear-contaminated iodine-containing wastewater and steam, as well as the recycling of the material.
[0065] Based on the above-described preferred embodiments of the present invention, and through the foregoing description, those skilled in the art can make various changes and modifications without departing from the inventive concept. The technical scope of this invention is not limited to the contents of the specification.
Claims
1. A triangular amine macrocyclic adsorbent material, characterized in that, The general structural formula of the triangular amine macrocyclic adsorbent material is either Formula I or Formula II: ； ； In the formula, It is any one of the following groups: .
2. The triangular amine macrocyclic adsorbent material according to claim 1, characterized in that, The structural formula of the triangular amine macrocyclic adsorbent material is any one of the following: ； 。 3. A method for synthesizing the triangular amine macrocyclic adsorbent material as described in claim 1 or 2, characterized in that, Includes the following steps: Compound A, 4-formylphenylboronic acid, palladium catalyst and sodium carbonate were mixed and a first solvent was added as the reaction system to obtain a mixture; The mixture was refluxed to produce a precipitate, which was then purified to obtain intermediate B. Intermediate B and 1,2-cyclohexanediamine were dissolved in a second solvent and refluxed. After the reaction was completed, the mixture was purified to obtain the triangular amine macrocyclic adsorbent material shown in Formula I. The general structural formula of compound A is as follows: The general structural formula of the intermediate B is as follows: In the formula, The definition is as described in claim 1 or 2.
4. The method for synthesizing the triangular amine macrocyclic adsorbent material according to claim 3, characterized in that, It also includes the following steps: The triangular amine macrocyclic adsorbent material shown in Formula I was dissolved in a third solvent, and sodium borohydride was added under ice bath for reflux reaction. After the reaction was completed, the triangular amine macrocyclic adsorbent material shown in Formula II was obtained by purification.
5. The method for synthesizing the triangular amine macrocyclic adsorbent material according to claim 3, characterized in that, The palladium catalyst is tetra(triphenylphosphine)palladium.
6. The method for synthesizing the triangular amine macrocyclic adsorbent material according to claim 3, characterized in that, The first solvent is a mixture of toluene, ethanol and water.
7. The method for synthesizing the triangular amine macrocyclic adsorbent material according to claim 3, characterized in that, The second solvent is a mixture of chloroform and methanol.
8. The method for synthesizing the triangular amine macrocyclic adsorbent material according to claim 4, characterized in that, The third solvent is a mixture of chloroform and methanol.
9. The application of a triangular amine macrocyclic adsorbent material as described in claim 1 or 2 in iodine adsorption.
10. The application of a triangular amine macrocyclic adsorbent material as described in claim 1 or 2 in nuclear waste treatment.
Citation Information
Patent Citations
Thiophene-based imine-linked covalent organic framework for iodine adsorption
CN118667105A
Substituted trianglamine and uses thereof
WO2024133779A1