WO2021253774A1

WO2021253774A1 - Radiophotoluminescent material and preparation method and use

Info

Publication number: WO2021253774A1
Application number: PCT/CN2020/137814
Authority: WO
Inventors: 刘汉洲; 覃皓明; 王殳凹
Original assignee: 苏州大学
Priority date: 2020-06-18
Filing date: 2020-12-19
Publication date: 2021-12-23
Also published as: CN111574727A

Abstract

A preparation method of a radiophotoluminescent material, comprising the following steps: mixing a soluble metal salt, a ligand and a solvent to obtain a mixed solution, and synthesizing a metal organic framework crystal from the mixed solution by using a solvothermal method. The radiation detection limit of the radiophotoluminescent material is wider, and the upper limit of the detectable radiation is 3700Gy.

Description

Radiation photoluminescence material and preparation method and application

Technical field

The present invention relates to the field of nuclear radiation technology, in particular to a radiation photoluminescence material, and a preparation method and application.

Background technique

With the development of nuclear science and technology, the demand for accurate radiation dosimeters in the fields of radiotherapy, radiodiagnosis and radiation protection is increasing day by day. Compared with real-time radiation detection equipment such as ionization chambers, scintillators, and semiconductors, solid dosimeters have the characteristics of small size, continuous monitoring, and separation of test and read signals, which play an irreplaceable role in radiation dose testing.

At present, the field of solid radiation dosimeters mainly includes three types of dosimeters: thermoluminescence, optical luminescence and radioluminescence. Thermoluminescence dosimeters and optical luminescence dosimeters use thermal excitation or light excitation to recombine electron-hole pairs generated by radiation to induce fluorescence, which is limited by poor signal stability under photothermal conditions. The radiophotoluminescence dosimeter uses the new energy level generated by the radiation defect to read the signal through ultraviolet excitation. Since the new energy level will not disappear after being excited, it has the ability to be read repeatedly, and the signal is being read. No obvious attenuation occurs during the fetching process. Traditional radiant photoluminescent materials mainly use silver-doped phosphate glass and Al ₂ O ₃ :C. Most of the related researches focus on material doping modification to enhance part of the radiation detection performance, and few new materials have been found to be suitable for radiant light. Luminescence detection has problems such as limited optional materials, low radiation dose test upper limit, and limited application scenarios. Therefore, it is necessary to develop a new material with radiative photoluminescence properties.

Metal-organic framework (MOF) materials are metal-organic hybrids with high crystallinity. Organic ligands can modify various groups and have high designability. Due to its unique frame structure, its gas adsorption, separation, catalysis, fluorescence and other properties have been extensively studied. The metal part can have a higher radiation blocking ability, which can significantly improve the radiation detection efficiency. The selection of luminescent components in the organic part has proved to be beneficial to the design of high quantum yield MOF materials, which have good application prospects in the field of radiation detection, but the current applications are still few.

Summary of the invention

The technical problem to be solved by the present invention is to provide a new type of radiation photoluminescence material that can increase the upper limit of detection of radiation dose, and a preparation method and application thereof.

In order to solve the above technical problems, the present invention provides a method for preparing a radiation photoluminescent material, which includes the following steps:

The soluble metal salt, the ligand and the solvent are mixed to obtain a mixed solution, the metal organic framework crystals are synthesized by solvothermal method on the mixed solution, and the metal organic framework crystals are washed and dried to obtain a radiation photoluminescent material, wherein the The molar ratio of the soluble metal salt to the ligand is 1:10-10:1, the benzene ring of the ligand is connected with a methyl group, and the valence state of the soluble metal salt is divalent and/or trivalent.

The preparation method of the above-mentioned radiant photoluminescence material is simple. It only needs to mix the soluble metal salt, the methyl-attached ligand on the benzene ring and the solvent, and synthesize the metal organic framework crystal by solvothermal method, and then compare the metal organic framework The crystal is cleaned and dried to obtain a radiation photoluminescent material.

It has been verified by experiments that the highly crystalline metal organic framework crystals (MOF) are synthesized in the above-mentioned radiation photoluminescence material, which makes the radiation photoluminescence material have higher density and radiation blocking ability. The benzene ring of the ligand is connected The methyl group can make the above-mentioned radiant photoluminescent material accumulate the fluorescent signal generated by free radicals after irradiation, so that the radiant photoluminescent material has good radiant photoluminescence properties. Among them, the benzene ring is connected to the methyl group Compared with ligands with other groups (such as carboxyl) attached to the benzene ring, the ligand can accumulate and maintain the fluorescent signal generated by free radicals. In addition, the material also has a certain degree of light transmittance, excellent luminous efficiency and good mechanical strength. The fluorescent signal can be maintained for several days to several weeks.

Compared with traditional silver glass dosimeter materials, the radiation detection limit of the above-mentioned radioluminescent materials is larger, that is, the detection limit of radiation that can be detected is 3700Gy, while the detection limit of the preparation materials of traditional silver glass dosimeters is 10Gy.

In one embodiment, the soluble metal salt is selected from at least one of lead nitrate, lead chloride, barium nitrate, bismuth nitrate, calcium nitrate, gadolinium nitrate, zinc nitrate, europium nitrate, and terbium nitrate.

In one of the embodiments, the ligand is selected from the group consisting of 2-methylterephthalic acid, 2,5-dimethylterephthalic acid, 2,6-dimethylterephthalic acid, and tetramethylterephthalic acid. At least one of phthalic acid and 4-methyl-2,6-naphthalenedicarboxylic acid. Compared with the ligands with other groups (for example: carboxyl) attached to the benzene ring of the above ligands, which have a methyl group attached to the benzene ring, they can accumulate and maintain the fluorescent signal generated by the free radicals.

In one embodiment, the solvent is selected from at least one of N,N-dimethylformamide, dimethylsulfoxide, N,N-dimethylacetamide, ethanol and water.

In one of the embodiments, in the step of synthesizing metal organic framework crystals by solvothermal method, the temperature of the solvothermal is 60-140°C.

In one of the embodiments, the synthesis time is 3-7 days.

In one of the embodiments, in the step of mixing the soluble metal salt, the ligand, and the solvent to obtain the mixed solution, the method further includes performing ultrasonic treatment on the mixed solution.

In one of the embodiments, the frequency of the ultrasonic treatment is 33-40 kHz.

The present invention also provides a radiophotoluminescent material prepared by the method for preparing radiophotoluminescence according to any one of the present invention.

The present invention also provides an application of the radiation photoluminescence material according to the present invention in the preparation of a radiation photoluminescence dosimeter.

Description of the drawings

Figure 1 is a radiometric diagram of the radioluminescent material in Example 1 of the present invention;

Figure 2 is a radiometric diagram of the radioluminescent material in Comparative Example 2 of the present invention;

Figure 3 is a radiometric diagram of the radiophotoluminescent material in Comparative Example 3 of the present invention.

detailed description

In order to make the above-mentioned objects, features and advantages of the present invention more obvious and understandable, the specific embodiments of the present invention will be described in detail below with reference to the accompanying drawings. In the following description, many specific details are explained in order to fully understand the present invention. However, the present invention can be implemented in many other ways different from those described herein, and those skilled in the art can make similar improvements without departing from the connotation of the present invention. Therefore, the present invention is not limited by the specific embodiments disclosed below.

Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by those skilled in the technical field of the present invention. The terms used in the specification of the present invention herein are only for the purpose of describing specific embodiments, and are not intended to limit the present invention. The term "and/or" as used herein includes any and all combinations of one or more related listed items.

Example 1

A preparation method of radiant photoluminescence material includes the following steps:

Mix 0.01 mmol of lead nitrate and 0.1 mmol of 2-methylterephthalic acid in a 5 mL scintillation vial, and then add 2 mL of N,N-dimethylformamide. Ultrasound dissolves and disperses the powder uniformly, and the ultrasonic frequency is 33kHz. Tighten the lid of the scintillation vial, put it in an oven at 140°C, and let it stand for 3 days to generate metal organic framework crystals. Take out the metal organic frame crystal, clean the surface of the metal organic frame crystal 3 times with N,N-dimethylformamide and ethanol, and dry at room temperature to obtain the product radiation photoluminescent material.

Example 2

Mix 0.05mmol of lead chloride, 0.05mmol of barium nitrate and 0.01mmol of 2,5-dimethylterephthalic acid in a 10mL scintillation vial, add 1mL of N,N-dimethylformamide and 1mL of water. Ultrasound dissolves and disperses the powder uniformly, and the ultrasonic frequency is 35kHz. Tighten the lid of the scintillation vial, put it in an oven at 80°C, and let it stand for 3 days to generate metal organic framework crystals. Take out the metal organic frame crystal, clean the surface of the metal organic frame crystal 3 times with N,N-dimethylformamide and ethanol, and dry at room temperature to obtain the product radiation photoluminescent material.

Example 3

Mix 0.05mmol of bismuth nitrate, 0.05mmol of calcium nitrate, 0.1mmol of 2,5-dimethylterephthalic acid, and 0.1mmol of 4-methyl-2,6-naphthalenedicarboxylic acid in a 5mL scintillation vial, Add 0.5 mL of N,N-dimethylformamide and 1 mL of dimethyl sulfoxide. Ultrasound dissolves and disperses the powder evenly, and the ultrasonic frequency is 40kHz. Tighten the lid of the scintillation vial, put it in an oven at 60°C, and let it stand for 3 days to generate metal organic framework crystals. Take out the metal organic frame crystal, clean the surface of the metal organic frame crystal 3 times with N,N-dimethylformamide and ethanol, and dry at room temperature to obtain the product radiation photoluminescent material.

Example 4

Combine 0.05mmol of barium nitrate, 0.05mmol of zinc nitrate, 0.05mmol of europium nitrate, 0.05mmol of 2,6-dimethylterephthalic acid, and 0.05mmol of 2,5-dimethylterephthalic acid in 5mL Mix in a scintillation vial, and add 1.5 mL of N,N-dimethylformamide and 1 mL of ethanol. Ultrasound dissolves and disperses the powder uniformly, and the ultrasonic frequency is 33kHz. Tighten the lid of the scintillation vial, put it in an oven at 80°C, and let it stand for 5 days to generate metal organic framework crystals. Take out the metal organic frame crystal, clean the surface of the crystal with N,N-dimethylformamide and ethanol 3 times, and dry it at room temperature to obtain the product radiation photoluminescent material.

Example 5

Mix 0.05mmol of gadolinium nitrate, 0.05mmol of terbium nitrate, 0.1mmol of 4-methyl-2,6-naphthalenedicarboxylic acid, and 0.05mmol of tetramethylterephthalic acid in a 20mL scintillation vial, and add 5mL of N,N-dimethylformamide and 5 mL of water. Ultrasound dissolves and disperses the powder uniformly, and the ultrasonic frequency is 33kHz. Tighten the lid of the scintillation vial, put it in an oven at 80°C, and let it stand for 7 days to generate metal organic framework crystals. Take out the metal organic frame crystal, clean the surface of the metal organic frame crystal 3 times with N,N-dimethylformamide and ethanol, and dry at room temperature to obtain the product radiation photoluminescent material.

Comparative example 1

Silver glass dosimeter materials can be purchased from CHIYADA company.

Comparative example 2

A preparation method of radiant photoluminescence material, the preparation method is basically the same as that of Example 1, except that the ligand is selected from 2,5-dihydroxyterephthalic acid. After testing, there is no radiant photoluminescence. Luminous phenomenon.

Comparative example 3

A preparation method of a radiant photoluminescence material. The preparation method is basically the same as that of Example 1, except that the ligand is selected from terephthalic acid. After testing, there is no radiant photoluminescence phenomenon.

Effectiveness verification

A CRAIC solid-state spectrometer was used to perform radiophotoluminescence detection on the radioluminescent material synthesized in the embodiment of the present invention, and the detection results are shown in Table 1 below.

Table 1

组别Group	辐射测量上限(Gy)Upper limit of radiation measurement (Gy)
实施例1Example 1	36573657
实施例2Example 2	10071007
实施例4Example 4	477477
对比例1(银玻璃剂量计材料)Comparative example 1 (silver glass dosimeter material)	1010
对比例2Comparative example 2	无信号响应No signal response
对比例3Comparative example 3	无信号响应No signal response

Combining Figure 1 and Table 1, it can be seen that the upper limit of the radiation value detected by the synthetic radiation photoluminescent material in the example group of the present invention is far greater than the upper limit of the radiation value of the comparative example group 1 (silver glass dosimeter material), combined with Figure 2 As shown in Fig. 3, the synthetic radioluminescent materials in Comparative Example 2 and Comparative Example 3 have no signal response, which means that the radioluminescent materials in Comparative Example 2 and Comparative Example 3 have no radiative photoluminescence phenomenon.

The technical features of the above-mentioned embodiments can be combined arbitrarily. In order to make the description concise, all possible combinations of the various technical features in the above-mentioned embodiments are not described. However, as long as there is no contradiction in the combination of these technical features, All should be considered as the scope of this specification.

The above-mentioned embodiments only express several implementation modes of the present invention, and their description is relatively specific and detailed, but they should not be understood as a limitation on the scope of the invention patent. It should be pointed out that for those of ordinary skill in the art, without departing from the concept of the present invention, several modifications and improvements can be made, and these all fall within the protection scope of the present invention. Therefore, the protection scope of the patent of the present invention should be subject to the appended claims.

Claims

A preparation method of radiant photoluminescence material, which is characterized in that it comprises the following steps:

The soluble metal salt, the ligand and the solvent are mixed to obtain a mixed solution, the metal organic framework crystals are synthesized by solvothermal method on the mixed solution, and the metal organic framework crystals are washed and dried to obtain a radiation photoluminescent material, wherein the The molar ratio of the soluble metal salt to the ligand is 1:10-10:1, the benzene ring of the ligand is connected with a methyl group, and the valence state of the soluble metal salt is divalent and/or trivalent.
The method for preparing a radiation photoluminescent material according to claim 1, wherein the soluble metal salt is selected from the group consisting of lead nitrate, lead chloride, barium nitrate, bismuth nitrate, calcium nitrate, gadolinium nitrate, zinc nitrate, nitric acid At least one of europium and terbium nitrate.
The method for preparing a radiation photoluminescent material according to claim 1, wherein the ligand is selected from the group consisting of 2-methylterephthalic acid, 2,5-dimethylterephthalic acid, 2,6 -At least one of dimethyl terephthalic acid, tetramethyl terephthalic acid, and 4-methyl-2,6-naphthalenedicarboxylic acid.
The method for preparing a radiation photoluminescent material according to any one of claims 1 to 3, wherein the solvent is selected from the group consisting of N,N-dimethylformamide, dimethylsulfoxide, N,N- At least one of dimethylacetamide, ethanol and water.
The method for preparing a radiation photoluminescent material according to any one of claims 1 to 3, wherein in the step of synthesizing metal organic framework crystals by solvothermal method, the temperature of the solvothermal is 60-140°C .
The method for preparing a radiation photoluminescent material according to any one of claims 1-3, wherein the synthesis time is 3-7 days.
The method for preparing a radiation photoluminescent material according to any one of claims 1 to 3, characterized in that, in the step of mixing the soluble metal salt, the ligand and the solvent to obtain the mixed solution, the method further comprises: Perform sonication.
8. The method for preparing a radiant photoluminescent material according to claim 7, wherein the frequency of the ultrasonic treatment is 33-40 kHz.
A photoluminescent material prepared by the method for preparing photoluminescence according to any one of claims 1-8.
The use of the radiophotoluminescent material of claim 9 in the preparation of a radiophotoluminescent dosimeter.