CPN-Y2-Cl cation framework material as well as preparation method and application thereof

Abstract

The invention discloses a CPN-Y2-Cl cation framework material as well as a preparation method and application thereof. The CPN-Y2-Cl cation framework material is constructed by carrying out quaternization reaction on tetra (1-imidazole phenyl) ethylene and 5, 5 '-bromomethyl-2, 2'-dipyridyl, and is obtained by carrying out anion exchange. The material has rapid and efficient adsorption performance on I3 <-> in a water phase, and still shows good selectivity in the presence of various competitive anions. Meanwhile, the material has obvious fluorescence quenching in the process of acting with I3 <->, and rapid detection of I3 <-> in water can be realized. The material designed by the invention is stable in performance, the preparation process is simple and convenient, and the prepared organic cation framework material has dual functions of adsorption and fluorescence recognition, and has a wide application prospect in the fields of treatment and real-time monitoring of radioactive iodine polluted water.

Description

Technical Field

[0001] This application relates to the field of biomedical technology, specifically to a CPN-Y2-Cl cation framework material, its preparation method, and its application. Background Technology

[0002] Iodine is a key element in the nuclear industry and medical radiation fields, and its radioactive isotopes (such as...) 129 I and 131 I) It possesses significant environmental mobility and bioaccumulation characteristics, making it one of the pollutants that urgently require key attention during nuclear wastewater treatment. Among them, 129 I has an extremely long half-life (approximately 1.57 × 10⁻⁶). 7 With its long lifespan (years) and strong migration ability, it can persist in the environment for a long time and spread into the ecosystem through water bodies. 131 Although iodine (I) has a short half-life, it has high biological activity and tends to accumulate in the human thyroid gland, potentially causing metabolic disorders, tissue damage, and even death. During nuclear accidents, nuclear waste disposal, and the use of medical radiation sources, radioactive iodine ions readily combine with elemental iodine to form I3. - Radioactive iodine can easily enter the water circulation system, causing water pollution. Therefore, achieving efficient removal and safe monitoring of radioactive iodine in aqueous solutions is of great significance for nuclear safety, ecological environmental protection, and public health.

[0003] Compared to traditional inorganic adsorbents such as silver-based zeolites, activated carbon, and clay minerals, organic cation frameworks (CPNs) contain stable positively charged sites within their framework. These CPNs can attract negatively charged I₃ molecules through electrostatic interactions, ion exchange, and various non-covalent interactions. - This enables more efficient adsorption. Furthermore, these materials typically possess designable pore structures and good aqueous stability, demonstrating potential advantages in aquatic environments.

[0004] Besides pollutant removal, rapid and sensitive identification of polyiodide ions in water is also a significant practical need. Fluorescent recognition technology, due to its fast response, high sensitivity, and ease of operation, is suitable for on-site detection and real-time early warning of radioactive pollutants. By introducing the fluorescent unit tetraphenylethylene into an organic cation framework material, the material can adsorb I3... - The process produces detectable fluorescence changes, thereby enabling the detection of I3. - Visual recognition. Summary of the Invention

[0005] (a) Purpose of the invention

[0006] The purpose of this application is to provide a cationic framework material CPN-Y2-Cl that combines highly efficient adsorption and fluorescence recognition functions, enabling the adsorption of I3 in aqueous phases.- It can remove substances quickly, efficiently, and selectively.

[0007] (II) Technical Solution

[0008] The first aspect of this application provides a CPN-Y2-Cl cationic framework material, the chemical structural formula of which is as follows:

[0009] .

[0010] A second aspect of this application provides a method for preparing a CPN-Y2-Cl cation framework material, comprising the following steps:

[0011] The tetra(1-imidazolylphenyl)ethylene and 5,5'-bromomethyl-2,2'-bipyridine were subjected to a quaternization reaction to obtain the synthetic product;

[0012] The synthesized product was replaced with saturated sodium chloride to obtain the CPN-Y2-Cl cationic framework material.

[0013] The CPN-Y2-Cl cationic framework material provided in this application is obtained by quaternization reaction of large-sized aromatic conjugated monomer tetra(1-imidazolylphenyl)ethylene (TIPE) and 5,5'-bromomethyl-2,2'-bipyridine ((BrCH2)2Bpy), followed by saturated sodium chloride replacement. It is a type of organic cationic framework material formed by covalent bonds. By introducing quaternization ion sites into the nitrogen-rich porous organic polymer framework, the CPN-Y2-Cl cationic framework material exhibits positive electrical properties, thus enabling it to react with polyiodide anions (I3). - Effective electrostatic interactions are generated between them. Simultaneously, Cl in the skeleton... - Compatible with I3 - Ion exchange occurs, causing I3 to... - It can enter and be fixed in the porous skeleton, thereby achieving I3 - Highly efficient adsorption.

[0014] Preferably, the mass ratio of the tetra(1-imidazolylphenyl)ethylene to 5,5'-bromomethyl-2,2'-bipyridine is 1:(1.1-1.2).

[0015] Preferably, the temperature of the quaternization reaction is 85-100°C. 0 C; The quaternization reaction time is 3 h.

[0016] Preferably, the synthesized product is a pale yellow CPN-Y2-Br, and its chemical structural formula is as follows:

[0017] .

[0018] Preferably, the synthesized product is replaced with saturated sodium chloride by soaking in a saturated sodium chloride solution for 12-24 hours.

[0019] A third aspect of this application provides a CPN-Y2-Cl cation framework material, prepared according to the preparation method described above.

[0020] The fourth aspect of this application provides an application of the CPN-Y2-Cl cation framework material described above in the treatment of radioactive iodine-contaminated water.

[0021] The fifth aspect of this application provides a method for adsorbing polyiodide ions from radioactive iodine-contaminated water, comprising:

[0022] The CPN-Y2-Cl cation framework material was added to a material containing I3. - Stirring or shaking in water contaminated with radioactive iodine;

[0023] At regular intervals, the sample was filtered through a 0.22-0.45 μm microporous membrane, and I3 was measured using a UV-Vis spectrophotometer. - The concentration of the solution.

[0024] Preferably, the CPN-Y2-Cl cation framework material is controlled to react with I3 - The solution ratio is (10-50) mg: 10 ml.

[0025] (III) Beneficial Effects

[0026] This application provides a cationic framework material, CPN-Y2-Cl, which combines highly efficient adsorption and fluorescence recognition functions. This material constructs a stable cationic framework through a quaternization reaction, and then obtains a Cl-based framework via anion exchange. - As an ion-functionalized material, its preparation process is simple and mild, suitable for large-scale preparation, and can achieve the functionalization of aqueous I3. - Rapid, efficient, and selective removal. The material exhibits excellent adsorption kinetics in aqueous environments, enabling rapid removal of I3. - This material exhibits high removal rates and maintains good adsorption selectivity and anti-interference ability even in the presence of multiple competing anions. Simultaneously, this material demonstrates high adsorption efficiency for I3... - A significant fluorescence quenching response was generated during the process, and its fluorescence change was similar to that of I3. - The concentration exhibits a good linear relationship, thus achieving the desired effect on I3 in water. - Its rapid and sensitive detection has important application value in the fields of radioactive iodine contamination water treatment and environmental monitoring.

[0027] It should be understood that the implementation of any embodiment of this application does not imply the simultaneous possession or achievement of multiple or all of the aforementioned beneficial effects. Furthermore, the content described in the summary section is not intended to limit the key or essential features of the embodiments of this application, nor is it intended to restrict the scope of this application. Other features of this application will become readily apparent from the following description of the embodiments. Attached Figure Description

[0028] To more clearly illustrate the embodiments of this application or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly introduced below. Obviously, the drawings described below are merely exemplary, and those skilled in the art can derive other embodiments based on the provided drawings without creative effort.

[0029] The structures, proportions, sizes, etc. illustrated in this specification are only for the purpose of assisting those skilled in the art in understanding and reading the content disclosed herein, and are not intended to limit the conditions under which this application can be implemented. Therefore, they have no substantial technical significance. Any modifications to the structure, changes in the proportions, or adjustments to the size, without affecting the effects and purposes that this application can produce, should still fall within the scope of the technical content disclosed in this application.

[0030] Figure 1 This is a synthesis technology roadmap for the CPN-Y2-Cl cationic framework material of this application;

[0031] Figure 2 SEM images of the CPN-Y2-Cl cation framework material prepared in Example 1 at different magnifications, where the magnifications from top to bottom are 3k, 5k, and 10k;

[0032] Figure 3 This application relates to the CPN-Y2-Cl cation framework material for I3. - Schematic diagram of solution capture experiment, where (a) shows the capture of I3 by CPN-Y2-Cl under different initial concentration conditions. - (b) shows the UV-Vis absorption spectrum of the solution afterward; - Adsorption kinetics diagram;

[0033] Figure 4 This application relates to the CPN-Y2-Cl cation framework material for I3. - Schematic diagram of the anti-interference effect of solution capture, where (a) shows the effect of CPN-Y2-Cl on I3 in the presence of competing anions. - The impact of removal rate, of which I3 -(a) The concentration ratio of CPN-Y2-Cl to competing ions is 1:100; (b) shows the effect of CPN-Y2-Cl on I3 in the presence of competing ions. - The partition coefficient of adsorption (K) d (Compare, mL / g)

[0034] Figure 5 This is a schematic diagram of the fluorescence sensing and anti-interference experiments of the CPN-Y2-Cl cation framework material of this application, where (a) shows the addition of different concentrations of I3. - Then, the fluorescence emission spectrum of CPN-Y2-Cl, (b) is the percentage of quenching of CPN-Y2-Cl at 422 in the presence of various competing ions. Detailed Implementation

[0035] Exemplary embodiments of this application will now be described in more detail with reference to the accompanying drawings. While exemplary embodiments of this application are shown in the drawings, it should be understood that this application may be implemented in various forms and should not be limited to the embodiments set forth herein. Rather, these embodiments are provided to enable a more thorough understanding of this application and to fully convey the scope of this application to those skilled in the art.

[0036] All raw materials used in the embodiments of this application are commercially available products, and their specific specifications are described in the text. Unless otherwise stated, all parts are by weight.

[0037] This application provides a CPN-Y2-Cl cationic framework material, its preparation method, and its application. This CPN-Y2-Cl cationic framework material introduces ion sites into a nitrogen-rich porous organic polymer, and is composed of large-sized aromatic conjugated monomers tetra(1-imidazolylphenyl)ethylene (TIPE) and 5,5'-bromomethyl-2,2'-bipyridine ((BrCH2)2Bpy) at 85-100 °C. 0 Under C2O3 conditions, a quaternization reaction occurs, followed by saturated sodium chloride replacement to obtain CPN-Y2-Cl cationic framework materials. These are a class of organic cationic framework materials formed by covalent bonds. CPN-Y2-Cl cationic framework materials exhibit positive electrical properties by introducing quaternization ion sites into the nitrogen-rich porous organic polymer framework, thus enabling them to react with polyiodide anions (I3O4). - Effective electrostatic interactions are generated between them. Simultaneously, Cl in the skeleton... - Compatible with I3 - Ion exchange occurs, causing I3 to... - It can enter and be fixed in the porous skeleton, thereby achieving I3 - Highly efficient adsorption.

[0038] Its synthesis technical route is as follows Figure 1 As shown in the figure. The following is a detailed description with reference to the specific embodiments.

[0039] Example 1-1

[0040] Preparation of CPN-Y2-Cl cationic framework materials:

[0041] 59.77 mg TIPE and 68.40 mg (BrCH2)2Bpy were added to a 25 ml microwave reactor, followed by the addition of 20 ml acetonitrile. After sonication for 30 min, the mixture was irradiated with microwave at 90 °C. 0 After reacting at C for 3 h, a pale yellow product (CPN-Y2-Br) was obtained. After soaking the CPN-Y2-Br sample in a saturated sodium chloride (NaCl) solution for 24 h, a pale yellow powder was obtained, namely the CPN-Y2-Cl cationic framework material, with a yield of 72.34%.

[0042] Examples 1-2

[0043] The process is essentially the same as in Example 1-1, except that microwave irradiation at 85°C is used in the quaternization reaction. 0 C reaction for 3 hours.

[0044] Examples 1-3

[0045] The process is essentially the same as in Example 1-1, except that microwave irradiation of 100 μL was used in the quaternization reaction. 0 C reaction for 3 hours.

[0046] In this embodiment, the reaction temperature is preferably controlled at 90°C. 0 C, this temperature is close to the boiling point of acetonitrile, which can ensure the reaction proceeds fully while avoiding violent boiling or morphological runaway, thus facilitating the acquisition of structurally stable and reproducible products, such as... Figure 2 As shown in the figure, the SEM images all exhibit a uniform, regular spherical structure with a particle size of approximately 0.8 μm. The experiment shows that when the reaction time is shortened to 2 h, the reaction is not sufficiently carried out, resulting in a low yield. When the reaction time is increased to 4 h, the morphology of the product changes significantly, making it difficult to form a uniform spherical structure.

[0047] Example 2

[0048] CPN-Y2-Cl for I3 - Solution capture experiment:

[0049] I3 - The solution was prepared before the experiment by dissolving equal amounts of iodine (I₂) and potassium iodide (KI) in deionized water. - The concentration of the solution is 1 mmol / L. -1 I3 - Adsorption kinetics experiment: 10 mg of CPN-Y2-Cl was added to 10 ml of I3 -In the solution, the mixture was shaken on a shaker at room temperature, and filtered through a 0.22 μm microporous membrane at regular intervals. The I3 concentration was measured using a UV-Vis spectrophotometer. - The concentration of the solution.

[0050] like Figure 3 As shown in (a), CPN-Y2-Cl, within 0.5 min, has an effect on I3 - The removal rate reached 82.3%, and within 1 minute, it removed I3. - The removal rate reached 99.1%, and within 5 minutes, it removed I3. - The removal rate reached 99.9%, specifically CPN-Y2-Cl for I3 - The results of the adsorption time experiment are shown in Table 1.

[0051] Table 1. CPN-Y2-Cl and its effect on I3 - Adsorption time experimental results

[0052] Contact time (min) <![CDATA[I3 - Absorption rate (%) 0.5 82.3 1 99.1 3 99.4 5 99.9 8 99.9 10 99.9 15 99.9

[0053] like Figure 3 As shown in (b), the adsorption kinetic data agree well with the pseudo-second-order kinetic simulation, R 2 >0.99 indicates that CPN-Y2-Cl has a positive effect on I3 - The adsorption behavior is chemisorption.

[0054] To highlight the rapid adsorption characteristics of the material in this application, CPN-Y2-Cl was compared with representative advanced adsorption materials reported in the literature. Compared to iCON-4 (which requires 120 s to achieve 99% removal rate), it... And Zn-Vlm6 (requires 180 s to achieve 99% removal rate) Compared to H, CPN-Y2-Cl reduces the time required to achieve the same removal rate by approximately 50% and 66%, respectively. Furthermore, compared to H... C OF-7 (requires approximately 6 hours to achieve 99% removal rate) In comparison, the adsorption rate of CPN-Y2-Cl increased by orders of magnitude, demonstrating its superior performance in I3. - Significant advantages in rapid removal.

[0055] Example 3

[0056] CPN-Y2-Cl for I3 - Solution capture anti-interference experiment:

[0057] Prepare 10 mL containing I3 - (1 mM) and various competing ions (e.g., Br) - ,Cl - NO3- and SO4 2- A mixed solution containing all four competing ions (CPN-Y2-Cl, 50 mg) was added to the mixed solution and the solution was shaken at 180 r / min for 24 h until adsorption equilibrium was reached. The filtrate was filtered through a 0.45 μm microporous membrane and the spectrum of the filtrate was recorded using a UV spectrophotometer.

[0058] As shown in Table 2, in the presence of excess competing ions, CPN-Y2-Cl has a significant effect on I3. - The removal rate remained at 98.9%, indicating that CPN-Y2-Cl has good selectivity.

[0059] Table 2. CPN-Y2-Cl vs. I3 in the presence of different competing ions - Adsorption performance

[0060] Competing ions <![CDATA[I3 - Adsorption rate (%) <![CDATA[I3 - partition coefficient (mL / g) Comparison 99.9 999000 <![CDATA[Cl - ]]> 99.8 499000 <![CDATA[Br - ]]> 99.5 199000 <![CDATA[NO3 - ]]> 99.4 165667 <![CDATA[SO4 2- ]]> 99.6 249000 mix 98.9 89909

[0061] Generally, when the allocation coefficient (K) d >10 4 mL g -1 When this occurs, it indicates that the adsorbent has a good affinity for the target analyte. For example... Figure 4 As shown, even under conditions of excessive competing ions, the I3 adsorbed by CPN-Y2-Cl... - K d It is also far higher than 10 4 mLg -1 This indicates that CPN-Y2-Cl affects I3 - It has high affinity.

[0062] To further illustrate this selectivity, CPN-Y2-Cl was compared with representative adsorbents reported in the literature. Compared with Zn-Vlm6 (where I3 is present in the presence of competing ions),... - Removal rate > 94% And TCNO-MA CTC (J. Hazard. Mater., I3 under the condition of competing ions) - Removal rate > 93% In comparison, CPN-Y2-Cl maintains a higher I3 concentration under similar conditions. - Removal rate indicates its ability to remove I3 in complex ionic systems. - It offers better selectivity.

[0063] The above:

[0064] [1] Prince, Hassan A, Chandra S, et al. Super-fast iodine capture byan ionic covalent organic network (iCON) from aqueous and vapor media[J]. RSCSustainability, 2023, 1(3): 511-522.

[0065] [2] Gao X, Hu Q H, Shi Y Z, et al. Rationally designing imidazole-based coordination polymers with high adsorption capacity for removing iodine[J]. Chemical Engineering Journal, 2023, 468: 143838.

[0066] [3] Zhang M, Samanta J, Atterberry B A, et al. A Crosslinked IonicOrganic Framework for Efficient Iodine and Iodide Remediation in Water[J].Angewandte Chemie, 2022, 134(52): e202214189.

[0067] [4] Zhang L, Luo Y T, Fan J Q, et al. Efficient capture of iodine insteam and water media by hydrogen bond-driven charge transfer complexes[J].Journal of Hazardous Materials, 2024, 465: 133488.

[0068] Example 4

[0069] CPN-Y2-Cl fluorescence sensing and anti-interference experiment:

[0070] A CPN-Y2-Cl fluorescent stock solution (0.5 mg / mL) was prepared by dispersing CPN-Y2-Cl in ultrapure water and sonicating for 20 minutes to obtain a homogeneous suspension. This was done to investigate the relationship between CPN-Y2-Cl and I3. - The fluorescence response characteristics of the interaction were investigated by taking 100 μL of fluorescent stock solution and adding 200 μL of I3 at different concentrations. - The solution was transferred to a quartz cuvette and diluted with water to 2 mL; then the fluorescence emission spectrum in the range of 380–650 nm was measured at an excitation wavelength of 367 nm.

[0071] To investigate the role of CPN-Y2-Cl in competing ions (Ac - Cl - NO3 - SO4 2- CO3 2- HCO3 - PO4 3- ,Br - Interference with I3 - For selective fluorescence recognition, take 100 μL of fluorescence stock solution, add 200 μL of 1 M interference ion solution, transfer to a quartz cuvette, dilute with water to 2 mL, and record the fluorescence emission spectrum in the range of 380–650 nm.

[0072] I3 at different concentrations - The fluorescence spectrum of CPN-Y2-Cl was measured. For example... Figure 5 As shown in (a), the fluorescence intensity of CPN-Y2-Cl was observed to increase with I3. - The concentration decreased with increasing concentration, especially after adding 50 μM I3. - Subsequently, the fluorescence quenching rate of CPN-Y2-Cl reached as high as 88.92% (there is almost no fluorescence quenching in existing technologies). - (For example), while the fluorescence intensity of CPN-Y2-Cl is related to I3 - The concentrations showed a good linear relationship in the range of 10 to 50 μM, with a correlation coefficient as high as 0.996.

[0073] To explore the practical sensing applications of CPN-Y2-Cl under environmentally relevant conditions, the effect of CPN-Y2-Cl on I3 was investigated. - The selectivity, such as Figure 5 As shown in (b) above, the results show that I3 - It can significantly quench the light of CPN-2-Cl, while other ions have little effect on its fluorescence.

[0074] This application provides an organic cation framework material for aqueous triiodine ion adsorption and fluorescence recognition, and its preparation method. The material is constructed by quaternization of tetrakis(1-imidazolylphenyl)ethylene and 5,5'-bromomethyl-2,2'-bipyridine, followed by anion exchange to obtain CPN-Y2-Cl. This material exhibits good adhesion to I3+ ions in aqueous solution. - It exhibits rapid and efficient adsorption performance, and maintains good selectivity even in the presence of multiple competing anions. Simultaneously, the material reacts with I3... - A significant fluorescence quenching occurred during the reaction, and the fluorescence response was similar to that of I3. - The concentration exhibits a good linear relationship, enabling the control of I3 in water. - Rapid detection. The preparation process of this application is simple and the material properties are stable. The obtained organic cation framework material has both adsorption and fluorescence recognition functions, and has broad application prospects in the treatment and real-time monitoring of radioactive iodine-contaminated water.

[0075] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of this application, and are not intended to limit them. Although this application has been described in detail with reference to the foregoing embodiments, those skilled in the art should understand that modifications can still be made to the technical solutions described in the foregoing embodiments, or equivalent substitutions can be made to some of the technical features. Such modifications or substitutions do not cause the essence of the corresponding technical solutions to deviate from the spirit and scope of the technical solutions of the embodiments of this application.

Claims

1. A CPN-Y2-Cl cationic framework material, characterized in that, The chemical structural formula of the CPN-Y2-Cl cationic framework material is as follows: 。 2. A method for preparing a CPN-Y2-Cl cationic framework material, characterized in that, Includes the following steps: The tetra(1-imidazolylphenyl)ethylene and 5,5'-bromomethyl-2,2'-bipyridine were subjected to a quaternization reaction to obtain the synthetic product; The synthesized product was replaced with saturated sodium chloride to obtain the CPN-Y2-Cl cationic framework material.

3. The method for preparing the CPN-Y2-Cl cation framework material according to claim 2, characterized in that, The mass ratio of the tetra(1-imidazolylphenyl)ethylene to 5,5'-bromomethyl-2,2'-bipyridine is 1:(1.1-1.2).

4. The method for preparing the CPN-Y2-Cl cation framework material according to claim 2, characterized in that, The quaternization reaction is carried out at a temperature of 85-100°C. 0 C; The quaternization reaction time is 3 h.

5. The method for preparing the CPN-Y2-Cl cation framework material according to claim 2, characterized in that, The synthesized product is a pale yellow CPN-Y2-Br, and its chemical structural formula is as follows: 。 6. The method for preparing the CPN-Y2-Cl cation framework material according to claim 2, characterized in that, The synthesized product was replaced with saturated sodium chloride and soaked in a saturated sodium chloride solution for 12-24 hours.

7. A CPN-Y2-Cl cationic framework material, characterized in that, It is prepared according to any one of claims 2-6.

8. The application of the CPN-Y2-Cl cation framework material as described in claim 1 or 7 in the treatment of radioactive iodine-contaminated water.

9. A method for adsorbing polyiodide ions from radioactive iodine-contaminated water, characterized in that, include: Adding the CPN-Y2-Cl cation framework material as described in claim 1 or 7 to a material containing I3 - Stirring or shaking in water contaminated with radioactive iodine; At regular intervals, the sample was filtered through a 0.22–0.45 μm microporous membrane, and I3 was measured using a UV-Vis spectrophotometer. - The concentration of the solution.

10. The method according to claim 9, characterized in that, Controlling the CPN-Y2-Cl cation framework material with I3 - The solution ratio is (10~50) mg: 10 ml.

Images