Preparation method and application of functionalized hydrogen-bonded organic framework material induced by high-energy electron beam irradiation

Abstract

The present invention discloses a preparation method and application of a functionalized hydrogen-bonded organic framework material induced by high-energy electron beam irradiation, belonging to the technical field of new materials for environmental detection. Europium salt and hydrogen-bonded organic framework material are added to an aqueous solution, stirred evenly, the mixed solution is irradiated by high-energy electron beam irradiation, and the mixed solution after high-energy electron beam irradiation is centrifuged and cleaned with ethanol to obtain the functionalized hydrogen-bonded organic framework material induced by high-energy electron beam irradiation. The preparation method of the functionalized hydrogen-bonded organic framework material induced by high-energy electron beam irradiation provided by the present invention has the advantages of relatively simple operation, low cost, and large-scale preparation. The functionalized hydrogen-bonded organic framework material induced by high-energy electron beam irradiation prepared by the present invention has a double emission peak and can be self-calibrated for detection. The functionalized hydrogen-bonded organic framework material induced by high-energy electron beam irradiation prepared by the present invention exhibits stable optical properties. The functionalized hydrogen-bonded organic framework material induced by high-energy electron beam irradiation prepared by the present invention can better detect thorium in deionized water through resonance energy transfer effect and inner filtering effect.

Description

Technical Field

[0001] The present invention belongs to the technical field of new environmental detection materials, and in particular relates to a preparation method and application of a functionalized hydrogen-bonded organic framework material induced by high-energy electron beam irradiation. Background Art

[0002] Thorium is a naturally occurring radioactive element that accumulates in marine algae and marine animals. It is both chemically toxic and a radiation hazard. Once it enters the human body through the food chain or drinking water, it can affect changes in the human blood, cause cancer, and have genetic effects. Thorium pollution mainly comes from thorium-containing mines and rare earth industrial wastewater. Accurate detection of thorium plays an important role in the treatment of heavy metal thorium ion pollution in water bodies. Currently, methods for detecting thorium ions include visible light spectrophotometry, X-ray fluorescence spectroscopy, inductively coupled plasma-atomic emission spectroscopy, inductively coupled plasma-mass spectrometry, neutron activation analysis, electrochemical analysis, and many other methods. These methods all require the use of instruments for detection and lack convenience. The fluorescent color change detection method is a detection method using luminescent metal-organic framework materials, which has the advantages of visual and rapid detection.

[0003] To further enhance the performance of hydrogen-bonded organic frameworks (HOFs), the development of novel functionalized HOFs has become a research hotspot in materials science. Functionalized HOFs generally refer to a class of hybrid materials that are endowed with specific functionalities by introducing foreign functional species into the HOF framework or chemically modifying its organic building blocks. The residual hydrogen-bonding donor / acceptor units and their weak interactions (such as electrostatic interactions) within the HOF structure facilitate the incorporation of exogenous materials into the framework, thereby achieving functionalization. Functionalized HOFs also possess controllable pore sizes and highly ordered pore structures, which significantly enhance the encapsulation and stability of guest luminescent materials. Currently, functionalized HOFs are prepared primarily through three strategies: ion exchange, post-modification after coordination synthesis, and in situ synthesis. While widely used, existing preparation methods, most notably hydrothermal methods, still suffer from high reaction temperatures and slow reaction rates. Furthermore, the fluorescence properties of the resulting functionalized HOFs urgently need to be optimized to meet the demands of applications in sensing, catalysis, and other fields. Summary of the Invention

[0004] The purpose of the present invention is to provide a preparation method and application of a functionalized hydrogen-bonded organic framework material induced by high-energy electron beam irradiation, so as to solve the problems existing in the above-mentioned prior art.

[0005] One of the technical solutions provided by the present invention:

[0006] A functionalized hydrogen-bonded organic framework material (HOF-BTB) induced by high-energy electron beam irradiation is prepared by treating an aqueous solution containing europium salt and a hydrogen-bonded organic framework material with high-energy electron beam irradiation.

[0007] The second technical solution provided by the present invention is:

[0008] A method for preparing the above-mentioned functionalized hydrogen-bonded organic framework material induced by high-energy electron beam irradiation comprises the following steps: adding europium salt and hydrogen-bonded organic framework material into an aqueous solution, stirring evenly, irradiating the mixed solution by high-energy electron beam irradiation, washing the mixed solution after high-energy electron beam irradiation with ethanol, and centrifuging to obtain the functionalized hydrogen-bonded organic framework material induced by high-energy electron beam irradiation.

[0009] The mass ratio of the europium salt to HOF-BTB is (10-50):4.

[0010] Different amounts of added europium salt will further affect the europium content in the material, thereby affecting its optical properties and thorium detection performance.

[0011] The mass volume ratio of the HOF-BTB to water is 4 mg:1 mL.

[0012] The high energy electron beam irradiation is carried out in the form of 15 KGy / round to 90 KGy.

[0013] High-energy electron beam irradiation is a technique that modifies material properties through the interaction of high-energy electrons with matter. Electron beam irradiation can ionize or excite material molecules, releasing orbital electrons and forming reactive species such as free radicals. These changes restructure the original molecular structure. This process not only breaks existing chemical bonds but also promotes new chemical reactions, thereby optimizing material properties.

[0014] In the present invention, high energy electron beam stimulates europium nitrate to decompose and release Eu through radiolysis. 3+ ions, and trigger the radiolysis of solvent molecules to produce highly active free radicals (such as OH·, H·). These free radicals further promote Eu 3+ Combination with active sites in the HOFs framework (such as hydrogen bond donor / acceptor units, carboxyl groups). 3+ Through electrostatic interaction, coordination bond and hydrogen bond induction effect, it is firmly combined with the HOFs framework, giving it a stable functional structure. At the same time, the radiation effect of high-energy electron beam may also induce the adjustment of HOFs microstructure, optimize its pore environment, and provide a stable and stable functional structure for Eu. 3+ The embedding of Eu 3+The unique fluorescence properties of HOFs have been effectively introduced, significantly improving the optical properties of the material and making it potentially valuable for applications in the detection field. Compared to traditional chemical functionalization methods, high-energy electron beam irradiation offers advantages such as environmental friendliness, high reaction efficiency, and uniform distribution, providing a new, faster and more efficient approach for the preparation of functionalized HOFs.

[0015] The third technical solution provided by the present invention is:

[0016] The above-mentioned functionalized hydrogen bond organic framework material induced by high-energy electron beam irradiation is used in the detection of heavy metal ions.

[0017] The heavy metal ions are thorium ions.

[0018] Compared with the prior art, the present invention has the following advantages and technical effects:

[0019] The method for preparing a functionalized hydrogen-bonded organic framework material induced by high-energy electron beam irradiation provided by the present invention has the advantages of relatively simple operation, low cost, and large-scale production. The functionalized hydrogen-bonded organic framework material induced by high-energy electron beam irradiation prepared by the present invention has dual emission peaks and self-calibration detection characteristics. The functionalized hydrogen-bonded organic framework material induced by high-energy electron beam irradiation prepared by the present invention exhibits stable optical properties. The functionalized hydrogen-bonded organic framework material induced by high-energy electron beam irradiation prepared by the present invention can better detect thorium in deionized water through the resonance energy transfer effect and the internal filtering effect.

[0020] Compared to the traditional hydrothermal method or magnetic stirring method, the functionalized hydrogen-bonded organic framework material prepared by the present invention has better fluorescence properties under the same dosage conditions, and is more excellent in the detection effect of thorium in deionized water, proving that the irradiation modification effect is better, overcoming the shortcomings of the above-mentioned prior art. In addition, compared with the traditional functionalization method, the present invention adopts high-energy electron beam irradiation, which utilizes electron beams accelerated in a high-voltage electric field to irradiate the substance, causing the reaction system to heat up quickly and evenly while causing the interaction between high-energy electrons and the substance, thereby ionizing and exciting the molecules of various substances, initiating chemical reactions to improve the performance of the material. Therefore, the reaction has the characteristics of fast reaction speed, high energy utilization, sensitive reaction, short synthesis time, high efficiency and energy saving, and green environmental protection. BRIEF DESCRIPTION OF THE DRAWINGS

[0021] In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the following briefly introduces the drawings required for use in the embodiments. Obviously, the drawings described below are only some embodiments of the present invention. For ordinary technicians in this field, other drawings can be obtained based on these drawings without paying any creative work.

[0022] Figure 1 This is the X-ray diffraction pattern of the functionalized hydrogen-bonded organic framework material prepared in Example 1-3;

[0023] Figure 2 This is the excitation spectrum of the functionalized hydrogen-bonded organic framework material prepared in Example 1-3;

[0024] Figure 3 This is the emission spectrum of the functionalized hydrogen-bonded organic framework material prepared in Example 1-3;

[0025] Figure 4 The emission spectra of the hydrogen-bonded organic framework materials prepared in Example 1, Comparative Example 1 and Comparative Example 2 are shown;

[0026] Figure 5 This is a diagram showing the effect of Eu100-HOF prepared in Example 1 on detecting thorium in deionized water;

[0027] Figure 6 This is a diagram showing the effect of Eu100-HOF(SM) prepared in Comparative Example 1 on detecting thorium in deionized water;

[0028] Figure 7 This is a diagram showing the effect of detecting thorium in deionized water using the material Eu100-HOF (HM) prepared in Comparative Example 2;

[0029] Figure 8 This is a comparison chart of the detection effects of Eu100-HOF prepared in Example 1 and Eu100-HOF (HM) prepared in Comparative Example 2 in deionized water. DETAILED DESCRIPTION

[0030] Various exemplary embodiments of the present invention will now be described in detail. This detailed description should not be considered as limiting the present invention, but rather as a more detailed description of certain aspects, features, and embodiments of the present invention.

[0031] It should be understood that the terms described herein are intended only to describe particular embodiments and are not intended to limit the present invention. In addition, for numerical ranges herein, it should be understood that each intermediate value between the upper and lower limits of the range is also specifically disclosed. Each smaller range between any intermediate value within a stated value or stated range and any other stated value or intermediate value within the stated range is also encompassed by the present invention. The upper and lower limits of these smaller ranges may be independently included or excluded within the scope.

[0032] Unless otherwise indicated, all technical and scientific terms used herein have the same meaning as commonly understood by those skilled in the art. Although only preferred methods and materials are described herein, any methods and materials similar or equivalent to those described herein may also be used in the practice or testing of the present invention. All documents mentioned in this specification are incorporated by reference to disclose and describe the methods and / or materials associated with the documents. In the event of any conflict with any incorporated document, the contents of this specification shall prevail.

[0033] It will be apparent to those skilled in the art that various modifications and variations may be made to the specific embodiments described herein without departing from the scope or spirit of the invention. Other embodiments will be apparent to those skilled in the art from the description of the invention. The description and examples are intended to be exemplary only.

[0034] The words “include,” “including,” “have,” “contain,” etc. used in this document are open-ended terms, meaning including but not limited to.

[0035] Compared with the commonly used hydrothermal method with high temperature and slow reaction, the radiation induction method is an efficient means of material modification. It can directly act on the material through high-energy rays at room temperature and pressure or under specific conditions, triggering chemical reactions inside the material, thereby changing the structure and properties of the material, and realizing an efficient, energy-saving and environmentally friendly synthesis process. Applying the radiation induction method to the preparation of HOFs functionalized materials is expected to achieve precise control of the structure and properties of HOFs materials by regulating the irradiation conditions and the amount of material added, and further improve its stability and functionalization level. In addition, this method is not only simple to operate and easy to precisely control the reaction conditions and product properties, but also the prepared materials usually have high purity, good dispersibility and excellent performance.

[0036] An embodiment of the present invention provides a functionalized hydrogen-bonded organic framework material induced by high-energy electron beam irradiation, which is prepared by treating an aqueous solution containing europium salt and the hydrogen-bonded organic framework material with high-energy electron beam irradiation.

[0037] An embodiment of the present invention also provides a method for preparing the above-mentioned functionalized hydrogen-bonded organic framework material induced by high-energy electron beam irradiation, comprising the following steps: adding europium salt and hydrogen-bonded organic framework material to an aqueous solution, stirring evenly, irradiating the mixed solution by high-energy electron beam irradiation, washing the mixed solution after high-energy electron beam irradiation with ethanol, and centrifuging to obtain the functionalized hydrogen-bonded organic framework material induced by high-energy electron beam irradiation.

[0038] In the following examples of the present invention, the europium salt is europium nitrate.

[0039] In the embodiments of the present invention, the mass ratio of the europium salt and the hydrogen-bonding organic framework material is (10-50):4. For example, in the following embodiments of the present invention, when the europium salt is europium nitrate, the usage ratios of the europium salt and the hydrogen-bonding organic framework material are 10:4, 20:4 and 50:4, respectively.

[0040] In an embodiment of the present invention, the mass volume ratio of the hydrogen-bonding organic framework material to water is 4 mg:1 mL.

[0041] In the embodiment of the present invention, the high energy electron beam irradiation is carried out in the form of 15 KGy / round to 90 KGy.

[0042] An embodiment of the present invention further provides the use of the functionalized hydrogen-bonded organic framework material induced by high-energy electron beam irradiation in detecting heavy metal ions, wherein the heavy metal ions are thorium ions.

[0043] In the present embodiment, HOF-BTB was prepared by mixing 22 mg of 1,3,5-tris(4-carboxyphenyl)benzene (H3BTB) with 5 mL of deionized water and 5 mL of ethanol in a 25 mL silica gel-lined screw-cap bottle. The mixture was ultrasonically treated for 5 minutes to obtain a uniform milky white solution. The solution was then transferred to an oven and maintained at 100°C for 48 hours. After cooling to room temperature, the solution was washed three times with ethanol by centrifugation and dried in a fume hood for 12 hours to obtain colorless powdery crystals, namely HOF-BTB.

[0044] Example 1

[0045] A method for preparing functionalized hydrogen-bonded organic framework materials induced by high-energy electron beam irradiation:

[0046] 1) Disperse 40 mg of HOF-BTB crystals and 100 mg of europium nitrate in 10 mL of deionized water and thoroughly sonicate to obtain a mixed solution;

[0047] 2) irradiating the mixed solution with a high-energy electron beam at a rate of 15 KGy / round to a maximum of 90 KGy;

[0048] 3) Centrifuging the mixed solution after high-energy electron beam irradiation in step 2), adding ethanol to the bottom product and centrifuging it, then adding ethanol to the bottom product, centrifuging the bottom product again, adding ethanol to the bottom product again, centrifuging at 6000 rpm for 5 minutes, collecting the bottom product after centrifugation, and obtaining a functionalized hydrogen bond organic framework material induced by high-energy electron beam irradiation, which is labeled as Eu100-HOF.

[0049] Example 2

[0050] A method for preparing functionalized hydrogen-bonded organic framework materials induced by high-energy electron beam irradiation:

[0051] 1) Disperse 40 mg of HOF-BTB crystals and 200 mg of europium nitrate in 10 mL of deionized water and thoroughly sonicate to obtain a mixed solution;

[0052] 2) irradiating the mixed solution with a high-energy electron beam at a rate of 15 KGy / round to a maximum of 90 KGy;

[0053] 3) Centrifuging the mixed solution after high-energy electron beam irradiation in step 2), adding ethanol to the bottom product and centrifuging it, then adding ethanol to the bottom product, centrifuging the bottom product again, adding ethanol to the bottom product again, and centrifuging at 6000 rpm for 5 minutes to obtain a functionalized hydrogen-bonded organic framework material induced by high-energy electron beam irradiation, labeled as Eu200-HOF.

[0054] Example 3

[0055] A method for preparing functionalized hydrogen-bonded organic framework materials induced by high-energy electron beam irradiation:

[0056] 1) Dispersing 40 mg of HOF-BTB crystals and 500 mg of europium nitrate in 10 mL of deionized water and thoroughly sonicating to obtain a mixed solution;

[0057] 2) irradiating the mixed solution with a high-energy electron beam at a rate of 15 KGy / round to a maximum of 90 KGy;

[0058] 3) Centrifuging the mixed solution after high-energy electron beam irradiation in step 2), adding ethanol to the bottom product and centrifuging it, then adding ethanol to the bottom product, centrifuging the bottom product again, adding ethanol to the bottom product again, and centrifuging at 6000 rpm for 5 minutes to obtain a functionalized hydrogen-bonded organic framework material induced by high-energy electron beam irradiation, labeled as Eu500-HOF.

[0059] Comparative Example 1

[0060] Preparation method of functionalized hydrogen bond organic framework material induced by magnetic stirring

[0061] 1) Disperse 40 mg of HOF-BTB crystals and 100 mg of europium nitrate in 10 mL of deionized water and thoroughly sonicate to obtain a mixed solution;

[0062] 2) The mixed solution was magnetically stirred for 24 h;

[0063] 3) The mixed solution after magnetic stirring in step 2) was washed three times with ethanol, and then centrifuged at 6000 rpm for 5 minutes. The bottom product after centrifugation was collected to obtain a magnetic stirring method induced functionalized hydrogen bond organic framework material, which was labeled Eu100-HOF(SM).

[0064] Comparative Example 2

[0065] Preparation method of hydrothermal induced functionalized hydrogen bond organic framework material

[0066] 1) Disperse 40 mg of HOF-BTB crystals and 100 mg of europium nitrate in 10 mL of deionized water and thoroughly sonicate to obtain a mixed solution;

[0067] 2) heating the mixed solution at 60°C for 24 hours;

[0068] 3) Centrifuging the mixed solution after high-energy electron beam irradiation in step 2), adding ethanol to the bottom product and centrifuging it, then adding ethanol to the bottom product, centrifuging the bottom product again, adding ethanol to the bottom product again, centrifuging at 6000 rpm for 5 minutes, collecting the bottom product after centrifugation, and obtaining a hydrothermally induced functionalized hydrogen bond organic framework material, labeled as Eu100-HOF(HM).

[0069] Figure 1 This is the X-ray diffraction pattern of the functionalized hydrogen-bonded organic framework material prepared in Example 1-3;

[0070] Figure 2 This is the excitation spectrum of the functionalized hydrogen-bonded organic framework material prepared in Example 1-3;

[0071] Figure 3 This is the emission spectrum of the functionalized hydrogen-bonded organic framework material prepared in Example 1-3.

[0072] Figure 4 These are emission spectra of the hydrogen-bonded organic framework materials prepared in Example 1, Comparative Example 1, and Comparative Example 2.

[0073] Figure 1 The XRD diffraction peak positions of the functionalized hydrogen-bonded organic framework materials Eu100-HOF, Eu200-HOF, and Eu500-HOF induced by high-energy electron beam irradiation according to the present invention are basically not shifted, and no other impurities are generated, indicating that the functionalized hydrogen-bonded organic framework materials induced by high-energy electron beam irradiation prepared by the present invention do not affect the crystal skeleton.

[0074] Figure 2-3 The functionalized hydrogen bond organic framework material induced by high energy electron beam irradiation prepared by the present invention has stable optical properties. Figure 4It can be seen that the Eu100-HOF prepared by the present invention has a double emission peak compared to Eu100-HOF(SM), and the europium emission peak is more intense than that of Eu100-HOF(HM). It can be seen that the material induced by the magnetic stirring method does not produce an emission peak of europium ions, proving that the magnetic stirring method does not synthesize functionalized hydrogen-bonded organic framework materials. Although the functionalized hydrogen-bonded organic framework material induced by the hydrothermal method has a double emission peak characteristic, the emission peak belonging to the europium ion is not strong enough, indicating that the europium doping amount of the functionalized hydrogen-bonded organic framework material induced by the hydrothermal method is not as high as the europium doping amount of Example 1.

[0075] 2 mg of the hydrogen-bonded organic framework materials prepared in Example 1 and Comparative Examples 1-2 were weighed, ground, added to 3 mL of deionized water and 2 ppm of thorium nitrate solution, respectively, and ultrasonically homogenized. After aging for 1 hour, the emission spectrum was collected, and the average value of three groups was taken for each parallel test to observe the quenching effect of the thorium nitrate solution on the fluorescence emission peak in the material.

[0076] The effect of Eu100-HOF prepared in Example 1 on detecting thorium in deionized water is shown in the figure. Figure 5 It can be seen that in the experiment of detecting thorium in deionized water (excitation wavelength of 280nm, slit width of 1nm) of the functionalized hydrogen bond organic framework material Eu100-HOF prepared in this example, after aging for 1h, the emission spectrum of the material showed obvious quenching, indicating that the Eu100-HOF prepared in Example 1 has good thorium detection performance.

[0077] The effect of Eu100-HOF(SM) prepared in comparative example 1 on detecting thorium in deionized water is shown in FIG. Figure 6 It can be seen that in the experiment of detecting thorium in deionized water (excitation wavelength of 280nm, slit width of 1nm) prepared in this comparative example, the emission spectrum of the material did not show obvious quenching after aging for 1h, indicating that the prepared Eu100-HOF(SM) has no detection performance for thorium.

[0078] The effect diagram of the material Eu100-HOF (HM) prepared in comparative example 2 for detecting thorium in deionized water is shown in FIG. Figure 7 The comparison of the detection effect of Eu100-HOF prepared in Example 1 and Eu100-HOF (HM) prepared in Comparative Example 2 in deionized water is shown in FIG. Figure 8 It can be seen that the performance of functionalized hydrogen-bonded organic framework materials induced by high-energy electron beam irradiation in detecting thorium in deionized water is higher than that of functionalized hydrogen-bonded organic framework materials prepared by hydrothermal method.

[0079] Figure 5-8This indicates that the functionalized hydrogen-bonded organic framework material induced by high-energy electron beam irradiation prepared by the present invention can better detect thorium in deionized water through the resonance energy transfer effect and the inner filtering effect. Compared with Eu100-HOF (HM), the detection effect is more obvious.

[0080] The above are merely preferred embodiments of the present invention, but the scope of protection of the present invention is not limited thereto. Any changes or substitutions that can be easily conceived by a person skilled in the art within the technical scope disclosed in the present invention should be included in the scope of protection of the present invention. Therefore, the scope of protection of the present invention should be based on the scope of protection of the claims.

Claims

1. A functionalized hydrogen-bonded organic framework material induced by high-energy electron beam irradiation, characterized in that: It is prepared by irradiating an aqueous solution containing europium salt and hydrogen-bonded organic framework material with high-energy electron beam; The high energy electron beam irradiation is performed in the form of 15KGy / round to 90KGy; The hydrogen bond organic framework material is HOF-BTB.

2. A method for preparing the functionalized hydrogen-bonded organic framework material induced by high-energy electron beam irradiation according to claim 1, characterized in that: The following steps are involved: Europium salt and hydrogen-bonded organic framework material are added to an aqueous solution, stirred evenly, the mixed solution is irradiated by high-energy electron beam irradiation, and the mixed solution after high-energy electron beam irradiation is centrifugally cleaned with ethanol to obtain the functionalized hydrogen-bonded organic framework material induced by high-energy electron beam irradiation.

3. The method for preparing a functionalized hydrogen-bonded organic framework material induced by high-energy electron beam irradiation according to claim 2, characterized in that: The mass ratio of the europium salt to the hydrogen bond organic framework material is (10-50):

4.

4. The method for preparing a functionalized hydrogen-bonded organic framework material induced by high-energy electron beam irradiation according to claim 2, characterized in that: The mass volume ratio of the hydrogen bond organic framework material to water is 4 mg:1 mL.

5. Use of the functionalized hydrogen-bonded organic framework material induced by high-energy electron beam irradiation according to claim 1 in detecting heavy metal ions.

6. The use according to claim 5, characterized in that The heavy metal ions are thorium ions.

Images