CN111574727A - Radiation photoluminescence material, preparation method and application - Google Patents

Abstract

The invention discloses a radiation photoluminescence material, a preparation method and application thereof, wherein the preparation method of the radiation photoluminescence material comprises the following steps: mixing soluble metal salt, a ligand and a solvent to obtain a mixed solution, synthesizing a metal organic framework crystal by adopting a solvothermal method for the mixed solution, cleaning and drying the metal organic framework crystal to obtain the radiation photoluminescence material, wherein the molar ratio of the soluble metal salt to the ligand is 1:10-10:1, a 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 radiation photoluminescence material prepared by the preparation method has wider radiation detection limit, namely the upper limit of detectable radiation is 3700Gy, while the upper limit of detectable radiation of the preparation material of the traditional silver glass dosimeter is only 10 Gy.

Description

A kind of radiation photoluminescent material, preparation method and application

technical field

The invention relates to the technical field of nuclear radiation, in particular to a radiation photoluminescent material, a preparation method and an 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, semiconductors, etc., solid dosimeters have the characteristics of small size, continuous monitoring, separation of test and read signals, etc., and play an irreplaceable role in radiation dose testing.

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

Metal-organic framework (MOF) materials, as metal-organic hybrids with high crystallinity, can modify various groups with organic ligands and have high designability. Due to its unique framework structure, its gas adsorption, separation, catalysis, fluorescence and other properties have been widely studied. The metal part can have a high radiation blocking ability, which can significantly improve the radiation detection efficiency. The selection of luminescent components in the organic part has been proved to be beneficial to the design of MOF materials with high quantum yields, 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 novel radiation photoluminescent material, a preparation method and an application thereof, which can increase the detection upper limit of the radiation dose.

In order to solve the above-mentioned technical problems, the present invention provides a preparation method of a radiation photoluminescent material, which comprises the following steps:

The soluble metal salt, the ligand and the solvent are mixed to obtain a mixed solution, a solvothermal method is used to synthesize a metal-organic framework crystal, and the metal-organic framework crystal is 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 radiation photoluminescent material is simple. It only needs to mix a soluble metal salt, a ligand connected to a methyl group on a benzene ring and a solvent, and use a solvothermal method to synthesize a metal organic framework crystal. The crystal is washed and dried to obtain a radiation photoluminescent material.

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

Compared with the traditional silver glass dosimeter material, the radiation detection limit of the above-mentioned radiation photoluminescent material is larger, that is, the upper limit of the radiation detection that can be detected is 3700Gy, while the detection limit of the preparation material of the traditional silver glass dosimeter 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 embodiment, the ligand is selected from the group consisting of 2-methylterephthalic acid, 2,5-dimethylterephthalic acid, 2,6-dimethylterephthalic acid, tetramethylterephthalic acid At least one of phthalic acid and 4-methyl-2,6-naphthalenedicarboxylic acid. The above-mentioned ligands all have methyl groups connected to the benzene ring, compared with the ligands connected with other groups (for example: carboxyl groups) on the benzene ring, which can accumulate and maintain the fluorescent signal generated by 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 embodiment, in the step of synthesizing the metal organic framework crystal by a solvothermal method, the temperature of the solvothermal method is 60-140°C.

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

In one embodiment, in the step of mixing the soluble metal salt, the ligand and the solvent to obtain a mixed solution, the mixed solution further includes ultrasonic treatment.

In one embodiment, the frequency of the sonication is 33-40 kHz.

The present invention also provides a radiation photoluminescent material prepared by the method for preparing radiation photoluminescence according to any one of the present inventions.

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

Description of drawings

1 is a radiation measurement diagram of the radiation photoluminescent material in Example 1 of the present invention;

2 is a radiation measurement diagram of the radiation photoluminescent material in Comparative Example 2 of the present invention;

FIG. 3 is a radiation measurement diagram of the radiation photoluminescent material in Comparative Example 3 of the present invention.

Detailed ways

In order to make the above objects, features and advantages of the present invention more clearly understood, the specific embodiments of the present invention will be described in detail below with reference to the accompanying drawings. In the following description, numerous specific details are set forth in order to provide a thorough understanding of 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 one of ordinary skill in the art to which this invention belongs. The terms used herein in the description of the present invention are for the purpose of describing specific embodiments only, and are not intended to limit the present invention. As used herein, the term "and/or" includes any and all combinations of one or more of the associated listed items.

Example 1

A preparation method of a radiation photoluminescent material, comprising the following steps:

0.01 mmol of lead nitrate and 0.1 mmol of 2-methylterephthalic acid were mixed in a 5 mL scintillation vial, followed by the addition of 2 mL of N,N-dimethylformamide. The powder was dissolved and uniformly dispersed by ultrasonic, and the ultrasonic frequency was 33 kHz. Tighten the cap of the scintillation vial and place it in an oven at 140 °C for 3 days to generate metal organic framework crystals. The metal organic framework crystal is taken out, the surface of the metal organic framework crystal is washed three times with N,N-dimethylformamide and ethanol, and dried at room temperature to obtain the product radiation photoluminescent material.

Example 2

A preparation method of a radiation photoluminescent material, comprising the following steps:

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

Example 3

A preparation method of a radiation photoluminescent material, comprising the following steps:

Mix 0.05 mmol of bismuth nitrate, 0.05 mmol of calcium nitrate and 0.1 mmol of 2,5-dimethylterephthalic acid, 0.1 mmol of 4-methyl-2,6-naphthalenedicarboxylic acid in a 5 mL scintillation vial, 0.5 mL of N,N-dimethylformamide and 1 mL of dimethylsulfoxide were added. Ultrasound dissolves the powder and disperses it uniformly, and the ultrasonic frequency is 40 kHz. Tighten the cap of the scintillation vial and place it in an oven at 60°C for 3 days to generate metal organic framework crystals. The metal organic framework crystal is taken out, the surface of the metal organic framework crystal is washed three times with N,N-dimethylformamide and ethanol, and dried at room temperature to obtain the product radiation photoluminescent material.

Example 4

A preparation method of a radiation photoluminescent material, comprising the following steps:

Put 0.05 mmol of barium nitrate, 0.05 mmol of zinc nitrate, 0.05 mmol of europium nitrate and 0.05 mmol of 2,6-dimethylterephthalic acid, 0.05 mmol of 2,5-dimethylterephthalic acid in 5 mL Mix in a scintillation vial and add 1.5 mL of N,N-dimethylformamide and 1 mL of ethanol. The powder was dissolved and uniformly dispersed by ultrasonic, and the ultrasonic frequency was 33 kHz. Tighten the cap of the scintillation vial and place it in an oven at 80 °C for 5 days to generate metal organic framework crystals. The metal organic framework crystal is taken out, the surface of the crystal is washed three times with N,N-dimethylformamide and ethanol, and dried at room temperature to obtain the product radiation photoluminescent material.

Example 5

A preparation method of a radiation photoluminescent material, comprising the following steps:

Mix 0.05 mmol of gadolinium nitrate, 0.05 mmol of terbium nitrate, 0.1 mmol of 4-methyl-2,6-naphthalenedicarboxylic acid, and 0.05 mmol of tetramethylterephthalic acid in a 20 mL scintillation vial, and add 5 mL of N,N-dimethylformamide and 5 mL of water. The powder was dissolved and uniformly dispersed by ultrasonic, and the ultrasonic frequency was 33 kHz. Tighten the cap of the scintillation vial and place it in an oven at 80 °C for 7 days to generate metal organic framework crystals. The metal organic framework crystal is taken out, the surface of the metal organic framework crystal is washed three times with N,N-dimethylformamide and ethanol, and dried at room temperature to obtain the product radiation photoluminescent material.

Comparative Example 1

Silver glass dosimeter material can be purchased from CHIYADA company.

Comparative Example 2

A preparation method of a radiation photoluminescent material, the preparation method is generally the same as that of Example 1, the difference is that the ligand is selected from 2,5-dihydroxyterephthalic acid, and after testing, no radiation photoluminescence luminous phenomenon.

Comparative Example 3

A preparation method of a radiation photoluminescent material, the preparation method is generally the same as that of Example 1, the difference is that the ligand is selected from terephthalic acid, and after testing, there is no radiation photoluminescence phenomenon.

Effect verification

A CRAIC solid-state spectrometer was used to perform radiation photoluminescence detection on the radiation photoluminescence materials synthesized in the examples of the present invention, and the detection results are shown in Table 1 below.

Table 1

group Radiation measurement upper limit (Gy) Example 1 3657 Example 2 1007 Example 4 477 Comparative example 1 (silver glass dosimeter material) 10 Comparative Example 2 no signal response Comparative Example 3 no signal response

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 embodiment 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). 3, the synthetic radiation photoluminescent materials in Comparative Example 2 and Comparative Example 3 have no signal response, indicating that the radiation photoluminescent materials in Comparative Examples 2 and 3 have no radiation photoluminescence phenomenon.

The technical features of the above-described embodiments can be combined arbitrarily. For the sake of brevity, all possible combinations of the technical features in the above-described embodiments are not described. However, as long as there is no contradiction between the combinations of these technical features, All should be regarded as the scope described in this specification.

The above-mentioned embodiments only represent several embodiments of the present invention, and the descriptions thereof are specific and detailed, but should not be construed 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 also be made, which all belong to 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 (10)

1. a preparation method of radiation photoluminescent material, is characterized in that, comprises the steps: The soluble metal salt, the ligand and the solvent are mixed to obtain a mixed solution, a solvothermal method is used to synthesize a metal-organic framework crystal, and the metal-organic framework crystal is 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. 2. 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, and zinc nitrate , at least one of europium nitrate and terbium nitrate. 3. The method for preparing a radiation photoluminescent material according to claim 1, wherein the ligand is selected from the group consisting of 2-methyl terephthalic acid, 2,5-dimethyl terephthalic acid, 2 , at least one of 6-dimethylterephthalic acid, tetramethylterephthalic acid and 4-methyl-2,6-naphthalene dicarboxylic acid. 4. the preparation method of radiation photoluminescent material as described in any one of claim 1-3, is characterized in that, described solvent is selected from N,N-dimethylformamide, dimethyl sulfoxide, N,N- At least one of N-dimethylacetamide, ethanol and water. 5. the preparation method of the radiation photoluminescent material as described in any one of claim 1-3, it is characterized in that, in adopting the step of solvothermal synthesis metal organic framework crystal, the temperature of described solvothermal is 60- 140°C. 6 . The preparation method of the radiation photoluminescent material according to claim 1 , wherein the synthesis time is 3-7 days. 7 . 7. The method for preparing a radiation photoluminescent material according to any one of claims 1 to 3, wherein in the step of mixing a soluble metal salt, a ligand and a solvent to obtain a mixed solution, the method further comprises: The mixture was sonicated. 8. The method for preparing a radiation photoluminescent material according to claim 7, wherein the frequency of the ultrasonic treatment is 33-40 kHz. 9. A radiation photoluminescent material prepared by the method for preparing radiation photoluminescence according to any one of claims 1 to 8. 10. The application of the radiation photoluminescence material of claim 9 in the preparation of radiation photoluminescence dosimeter.

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