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

Abstract

The invention discloses a preparation method and application of a functionalized hydrogen bond organic framework material induced by high-energy electron beam irradiation, and belongs to the technical field of new environmental detection materials.The preparation method comprises the steps that europium salt and a hydrogen bond organic framework material are added into an aqueous solution and stirred to be uniform, and the mixed solution is irradiated through high-energy electron beam irradiation to obtain the functionalized hydrogen bond organic framework material. And centrifugally cleaning the mixed solution subjected to high-energy electron beam irradiation with ethanol to obtain the high-energy electron beam irradiation induced functionalized hydrogen bond organic framework material. The preparation method of the functionalized hydrogen bond organic framework material induced by high-energy electron beam irradiation has the advantages of relatively simple operation, low cost, large-scale preparation and the like; the high-energy electron beam irradiation induced functionalized hydrogen bond organic framework material prepared by the invention has the characteristics of double emission peaks and self-calibration detection; the high-energy electron beam irradiation induced functionalized hydrogen bond organic framework material prepared by the invention shows stable optical properties; the high-energy electron beam irradiation induced functionalized hydrogen bond organic framework material prepared by the invention can better detect thorium in deionized water through a resonance energy transfer effect and an internal filtering effect.

Description

Technical Field

[0001] The 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 natural radioactive element that accumulates in marine algae and marine animals. Thorium is both chemically toxic and has radiation hazards. After entering the human body through the food chain or drinking water, it will affect the changes in human blood phase, and can cause cancer and genetic effects. Thorium pollution mainly comes from thorium-containing mines and rare earth industrial wastewater. The accurate detection of thorium plays an important role in the treatment of heavy metal thorium ion pollution in water bodies. At present, there are many methods for detecting thorium ions, including visible light spectrophotometry, X-ray fluorescence spectroscopy, inductively coupled plasma-atomic emission spectroscopy, inductively coupled plasma-mass spectrometry, neutron activation analysis, electrochemical analysis, etc. These methods all require the use of instruments for detection and lack convenience. The fluorescent color change detection method is a method of detection with the help of luminescent metal organic framework materials, which has the advantages of visual rapid detection.

[0003] In order to further improve the performance of hydrogen-bonded organic frameworks (HOFs), the development of new functionalized HOFs has become a research hotspot in the field of materials science. Functionalized HOFs generally refer to a class of hybrid materials that are endowed with specific functions by introducing foreign functional species into the framework structure of HOFs or chemically modifying its organic building blocks. The residual hydrogen-bonded donor / acceptor units in the HOFs structure and their weak interactions (such as electrostatic interactions) provide the possibility for the combination of exogenous substances with the framework, thereby achieving functional modification. Functionalized HOFs also have controllable pore size and highly ordered pore structure, which significantly improves the encapsulation and stability of guest luminescent substances. At present, the preparation of functionalized HOFs is mainly carried out through three strategies: ion exchange, post-modification after coordination synthesis, and in situ synthesis. Although the existing preparation methods represented by the hydrothermal method are widely used, they still have problems such as high reaction temperature and slow reaction rate. In addition, the fluorescence properties of the prepared functionalized HOFs need to be further optimized to meet their application needs 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 by high-energy electron beam irradiation.

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

[0008] A preparation method of 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, centrifuging, and obtaining 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 technology that changes the properties of materials through the interaction between high-energy electrons and matter. Electron beam irradiation can cause ionization or excitation of material molecules, thereby releasing orbital electrons and forming active species such as free radicals. These changes cause the original molecular structure to be reconstructed. This process not only destroys the original chemical bonds, but also promotes the occurrence of new chemical reactions, thereby optimizing the material properties.

[0014] In the present invention, high energy electron beam stimulates europium nitrate to decompose and release Eu through radiolysis. 3+ ions, and initiates the radiolysis of solvent molecules to produce highly active free radicals (such as OH·, H·). These free radicals further promote Eu 3+ Binding to active sites in the HOFs framework (such as hydrogen bond donor / acceptor units, carboxyl groups). 3+ Through electrostatic interaction, coordination bonds and the inductive effect of hydrogen bonds, 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 beams may also trigger the adjustment of the HOFs microstructure, optimize its pore environment, and provide a stable functional structure for Eu. 3+ The embedding of Eu 3+The unique fluorescence properties are effectively introduced into HOFs, which significantly improves the optical properties of the material and makes it have potential application value in the detection field. Compared with the traditional chemical functionalization method, high-energy electron beam irradiation has the advantages of being green, efficient, and evenly distributed, providing a new and efficient way to prepare functionalized HOFs materials.

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

[0016] The functionalized hydrogen-bonded 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 mass production. The functionalized hydrogen-bonded organic framework material induced by high-energy electron beam irradiation prepared by the present invention has the characteristics of double emission peaks and self-calibration 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 the resonance energy transfer effect and the inner filter effect.

[0020] Compared with 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 has a better detection effect on thorium in deionized water, proving that the irradiation modification effect is better, overcoming the shortcomings of the above-mentioned prior art. And compared with the traditional functionalization method, the present invention adopts high-energy electron beam irradiation, which utilizes electron rays accelerated in a high-voltage electric field to irradiate the substance, so that the reaction system is rapidly and evenly heated while causing the interaction between high-energy electrons and substances, 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 drawings required for use in the embodiments will be briefly introduced below. 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 creative labor.

[0022] Figure 1 This is an 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;

[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 the material Eu100-HOF (HM) prepared in Comparative Example 2 on detecting thorium in deionized water;

[0029] Figure 8 This is a comparison chart of the effects of Eu100-HOF prepared in Example 1 and Eu100-HOF (HM) prepared in Comparative Example 2 on detecting thorium 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 should be understood as a more detailed description of certain aspects, features, and embodiments of the present invention.

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

[0032] Unless otherwise indicated, all technical and scientific terms used herein have the same meanings as those generally understood by those skilled in the art. Although the present invention describes only preferred methods and materials, any methods and materials similar or equivalent to those described herein may also be used in the implementation 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 a conflict with any incorporated document, the content 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 of the present invention description without departing from the scope or spirit of the present invention. Other embodiments derived from the present invention description will be apparent to the skilled artisan. The present invention description and examples are 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, as an efficient material modification method, 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 performance 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 performance of HOFs materials by regulating the irradiation conditions and the amount of material added, and further improve its stability and functionalization level. Moreover, this method is not only simple to operate and easy to accurately control the reaction conditions and product properties, but also the prepared materials usually have high purity, good dispersibility and excellent performance.

[0036] The 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 by 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 the 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 in the form of 15 KGy / round to 90 KGy.

[0042] The embodiment of the present invention also 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] The preparation method of HOF-BTB in the embodiment of the present invention is to mix 22 mg of 1,3,5-tris(4-carboxyphenyl)benzene (H3BTB) with 5 mL of deionized water and 5 mL of ethanol solution, add them to a 25 mL silica gel lined screw cap bottle, and ultrasonically treat for 5 minutes to obtain a uniform milky white solution. Subsequently, the solution is transferred to an oven and kept at 100°C for 48 hours. After cooling to room temperature, it is centrifuged and washed three times with ethanol, 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 a functionalized hydrogen-bonded organic framework material induced by high-energy electron beam irradiation:

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

[0047] 2) subjecting the mixed solution to high-energy electron beam irradiation at a rate of 15 KGy / round to a dose 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 and centrifuging it again, adding ethanol to the bottom product again, centrifuging it at 6000 rpm for 5 minutes, collecting the bottom product after centrifugation, and obtaining a functionalized hydrogen-bonded organic framework material induced by high-energy electron beam irradiation, which is labeled as Eu100-HOF.

[0049] Example 2

[0050] A method for preparing a functionalized hydrogen-bonded organic framework material 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 ultrasonicate 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 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 and centrifuging it again, adding ethanol to the bottom product again and centrifuging it at 6000 rpm for 5 minutes to obtain a functionalized hydrogen-bonded organic framework material induced by high-energy electron beam irradiation, which is labeled as Eu200-HOF.

[0054] Example 3

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

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

[0057] 2) subjecting the mixed solution to high-energy electron beam irradiation at a rate of 15 KGy / round to a dose 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-bonded 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, and the bottom product after centrifugation was collected to obtain a magnetic stirring method induced functionalized hydrogen bond organic framework material, which was labeled as 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 h;

[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 and centrifuging it again, adding ethanol to the bottom product again, centrifuging it at 6000 rpm for 5 minutes, collecting the bottom product after centrifugation, and obtaining a hydrothermally induced functionalized hydrogen bond organic framework material, which is labeled as Eu100-HOF (HM).

[0069] Figure 1 This is an 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 It shows that the functionalized hydrogen-bonded 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 with Eu100-HOF (SM), and the europium emission peak is stronger than that of Eu100-HOF (HM); it can be seen that the material induced by the magnetic stirring method does not produce the 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 large as the europium doping amount of Example 1.

[0075] Weigh 2 mg of the hydrogen-bonded organic framework material prepared in Example 1 and Comparative Examples 1-2, grind them, add them to 3 mL of deionized water and 2 ppm of thorium nitrate solution, respectively, and ultrasonically homogenize them. 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 diagram of Eu100-HOF prepared in Example 1 detecting thorium in deionized water is shown in 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-bonded organic framework material Eu100-HOF prepared in this embodiment, after aging for 1h, the emission spectrum of the material has obvious quenching, indicating that Eu100-HOF prepared in Example 1 has good thorium detection performance.

[0077] The effect diagram of Eu100-HOF(SM) prepared in comparative example 1 for detecting thorium in deionized water is shown in 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, after aging for 1h, the emission spectrum of the material did not show obvious quenching, 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 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 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 filter effect. Compared with Eu100-HOF (HM), the detection effect is more obvious.

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

Claims

1. A functionalized hydrogen-bonded organic framework material induced by high-energy electron beam irradiation, characterized in that: The method is prepared by subjecting an aqueous solution containing europium salt and a hydrogen-bonded organic framework material to high-energy electron beam irradiation treatment.

2. A method for preparing a 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-bonding 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-bonding organic framework material to water is 4 mg:1 mL.

5. 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 high energy electron beam irradiation is carried out in the form of 15 KGy / round to 90 KGy.

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

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

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