Scintillating material, preparation method and use thereof

Abstract

A scintillating material, preparation method and use thereof are provided. The chemical formula of the scintillating material is C.sub.42H.sub.42X.sub.2MnO.sub.2P.sub.2, wherein X is selected from a group consisting of Cl and Br. The scintillating material has excellent X-ray scintillation performance and sensitive X-ray detection capability, and the detection limit of the scintillating material is far lower than the conventional medical diagnosis dose criterion of 5.50 ?Gy.sub.air/s. Compared with existing commercial scintillating materials, the scintillating material of the present application has remarkable superiority in performance, overcomes the defects of heavy metal pollution, high energy consumption and the like caused in the synthesis process of the scintillating material, and has important commercial application value in the field of green synthesis of high-performance scintillating materials.

Claims

1. A scintillating material, wherein a chemical formula of the scintillating material is shown in a Formula I:
C.sub.42H.sub.42X.sub.2MnO.sub.2P.sub.2Formula I wherein the X is selected from the group consisting of Cl and Br; wherein the scintillating material comprises two asymmetric structural units; wherein each of the two asymmetric structural units comprises a oxidized tris(o-methylphenyl)oxaphosphorus ligand, a semi-occupied Mn.sup.2+ ion, and an X ion; wherein a microscopic morphology of the scintillating material is a zero-dimensional structure.

2. The scintillating material according to claim 1, wherein in the scintillating material, the semi-occupied Mn.sup.2+ ion is in a tetrahedral spatial coordination structure.

3. The scintillating material according to claim 1, wherein a crystal structure of the scintillating material belongs to a monoclinic crystal system with a C2/c space group structure.

4. The scintillating material according to claim 1, wherein in the Formula I, the X is Cl; and among lattice parameters of the scintillating material, a=21.490 ?-21.496 ?, b=10.512 ?-10.518 ?, c=18.655 ?-18.671 ?, ?=110.67?-114.67?.

5. The scintillating material according to claim 1, wherein in the Formula I, the X is Br; and among lattice parameters of the scintillating material, a=18.586 ?-18.592 ?, b=10.614 ?-10.620 ?, c=21.916 ?-21.922 ?, ?=111.15?-115.15?.

6. The scintillating material according to claim 1, wherein among lattice parameters of the scintillating material, ?=90?, ?=90?, Z=4.

7. The scintillating material according to claim 1, wherein under an ultraviolet excitation with a wavelength in a range from 135 nm to 420 nm, an emission peak of the scintillating material is in a range from 510 nm to 514 nm, and an emission of the scintillating material is a green light emission.

8. The scintillating material according to claim 1, wherein a thermal decomposition temperature of the scintillating material is in a range from 275? C. to 285? C.

9. The scintillating material according to claim 1, wherein in the Formula I, the X is Cl; and a scintillation intensity of the scintillating material is 0.5 to 1 time a scintillation intensity of a bismuth germanate scintillating crystal.

10. The scintillating material according to claim 1, wherein in the Formula I, the X is Br; and a scintillation intensity of the scintillating material is 4 to 5 times a scintillation intensity of a bismuth germanate scintillating crystal; and the scintillation intensity of the scintillating material is 0.8 to 1.2 times a scintillation intensity of a lutetium-yttrium oxyorthosilicate scintillating crystal.

11. A method of preparing the scintillating material according to claim 1, comprising (1) mixing tris(o-methylphenyl)phosphorus with a solvent and a peroxide to obtain a mixture after an oxidation reaction; (2) adding a MnX.sub.2 metal salt to the mixture obtained in step (1) to obtain the scintillating material after a coordination reaction.

12. The method according to claim 11, wherein the solvent is at least one selected from the group consisting of ethanol, methanol, tetrahydrofuran, and N-methylpyrrolidone; and the peroxide is at least one selected from the group consisting of hydrogen peroxide, benzoyl peroxide, potassium peroxymonosulfate, potassium persulfate, ammonium peroxymonosulfate, and ammonium persulfate.

13. The method according to claim 11, wherein a molar ratio of the tris(o-methylphenyl)phosphorus to the peroxide to the MnX.sub.2 metal salt is (1-5):(2-10):(1-5).

14. The method according to claim 11, wherein in step (1), a reaction temperature of the oxidation reaction is in a range from 70? C. to 100? C.; and a reaction time of the oxidation reaction is in a range from 12 h to 24 h; in step (2), a reaction temperature of the coordination reaction is in a range from 80? C. to 100? C.; and a reaction time of the coordination reaction is in a range from 12 h to 24 h.

15. A use of the scintillating material according to claim 1 in an energetic particles detection and/or an imaging visualization; wherein energetic particles comprise X-rays.

16. The use according to claim 15, wherein a detection limit of the scintillating material is 3.90 ?Gy.sub.air/s when the scintillating material is C.sub.42H.sub.42C.sub.12MnO.sub.2P.sub.2.

17. The use according to claim 15, wherein a detection limit of the scintillating material is 0.82 ?Gy.sub.air/s when the scintillating material is C.sub.42H.sub.42Br.sub.2MnO.sub.2P.sub.2.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

(1) FIGS. 1A-1B are a schematic diagram of the crystal structure (without hydrogen atoms) of Sample 1-Cl.sup.# obtained in Example 1 and Sample 2-Br.sup.# obtained in Example 2, where FIG. 1A is the schematic diagram of the crystal structure of Sample 1-Cl.sup.#; and FIG. 1B is the schematic diagram of the crystal structure of Sample 2-Br.sup.#.

(2) FIGS. 2A-2B are a theoretical XRD diffraction pattern obtained by fitting the single crystal data of Sample 1-Cl.sup.# obtained in Example 1 and Sample 2-Br.sup.# obtained in Example 2 and its experimentally measured XRD diffraction pattern, where FIG. 2A is the theoretical XRD diffraction pattern obtained by fitting the single crystal data of Sample 1-Cl.sup.# and its experimentally measured XRD diffraction pattern; and FIG. 2B is the theoretical XRD diffraction pattern obtained by fitting the single crystal data of Sample 2-Br.sup.# and its experimentally measured XRD diffraction pattern.

(3) FIGS. 3A-3B are a thermal stability experimental profile of Sample 1-Cl.sup.# obtained in Example 1 and Sample 2-Br.sup.# obtained in Example 2, where FIG. 3A is the thermal stability experimental profile of Sample 1-Cl.sup.#; FIG. 3B is the thermal stability experimental profile of Sample 2-Br.sup.#.

(4) FIGS. 4A-4B are a photoluminescence experimental profile of Sample 1-Cl.sup.# obtained in Example 1 and Sample 2-Br.sup.# obtained in Example 2, including the optimal excitation wavelength and the optimal emission wavelength, where FIG. 4A is the photoluminescence experimental profile of Sample 1-Cl.sup.#; FIG. 4B is the photoluminescence experimental profile of Sample 2-Br.sup.#.

(5) FIGS. 5A-5B are an X-ray scintillation luminescence experimental profile of Sample 1-Cl.sup.# obtained in Example 1 and Sample 2-Br.sup.# obtained in Example 2, where FIG. 5A is the X-ray scintillation luminescence experimental profile of Sample 1-Cl.sup.#; FIG. 5B is the X-ray scintillation luminescence experimental profile of Sample 2-Br.sup.#.

(6) FIG. 6 is an experimental comparative plot of the scintillation performance of Sample 1-Cl.sup.# obtained in Example 1 and Sample 2-Br.sup.# obtained in Example 2.

(7) FIG. 7 is an experimental plot of Sample 1-Cl.sup.# obtained in Example 1 and Sample 2-Br.sup.# obtained in Example 2 against X-ray dose detection.

(8) FIG. 8 is the tetrahedral spatial coordination structure of the Mn2:

DETAILED DESCRIPTION OF THE EMBODIMENTS

(9) The present application will be described in detail below with reference to Examples, but the present disclosure is not limited to these Examples.

(10) Unless otherwise specified, the raw materials in the Examples of the present application were purchased commercially, in which tris(o-methylphenyl)phosphorus, manganese chloride, manganese bromide dihydrate were purchased from Meryer (Shanghai) Chemical Technology Co., Ltd.; protonaceous solvents such as ethanol and methanol, as well as peroxides including hydrogen peroxide, etc., were purchased from SINOPHARM.

Example 1 Preparation of Sample 1-Cl.SUP.#

(11) A mixed solution of 3 mmol of tris(o-methylphenyl)phosphorus in ethanol and hydrogen peroxide (18 mL, V:V=16:2) was placed at a reaction temperature of 100? C. for 12 hours and then cooled down to room temperature, and 3 mmol of a metal salt MnCl.sub.2 was added to continue the reaction at a reaction temperature of 100? C. for another 12 hours; after cooling, it was filtered, and crystals precipitated by placing the filtrate in an ether atmosphere for about a week, with a yield of 87% (based on MnCl.sub.2), and the chemical formula of the crystals was C.sub.42H.sub.42C.sub.12MnO.sub.2P.sub.2.

Example 2 Preparation of Sample 2-Br.SUP.#

(12) A mixed solution of 3 mmol of tris(o-methylphenyl)phosphorus in ethanol and hydrogen peroxide (18 mL, V:V=16:2) was placed at a reaction temperature of 100? C. for 12 hours and then cooled down to room temperature, and 3 mmol of a metal salt MnBr.sub.2.Math.2H.sub.2O was added to continue the reaction at a reaction temperature of 100? C. for another 12 hours; after cooling, bulk single crystals suitable for X-ray single-crystal diffraction experiments can be obtained directly; filtered, placed the filtrate in an ether atmosphere for about a week, and the crystals continued to precipitate with a yield of 91% (based on MnBr.sub.2.Math.2H.sub.2O), and the chemical formula of the crystals was C.sub.42H.sub.42Br.sub.2MnO.sub.2P.sub.2.

(13) Test Example 1 Structural Characterization of Samples

(14) Single crystal X-ray diffraction of Samples 1-Cl.sup.# and 2-Br.sup.# was carried out on a Mercury CCD-type single crystal diffractometer with a Mo target, a K? radiation source (?=0.7107 ?), and a test temperature of 293K. Structural resolution was carried out by Olex.sup.2 1.2. The test results are shown in FIG. 1A, one oxidized tris(o-methylphenyl)oxaphosphorus ligand, one semi-occupied Mn.sup.2+ ion and one Cl.sup.? ion were contained in the asymmetric unit; by symmetrization operation, it can be seen that Mn is a tetra-coordinated aberrant tetrahedral geometrical configuration, in which the MnCl bond length is 2.3303(6) ?, and the MnO bond length is 2.0494(14) ?; centered on Mn, the Cl1A-Mn1-Cl1 bond angle is 111.61(4?), the O1A-Mn1-Cl1A bond angle is 113.29(5), the O1-Mn1-C11A bond angle is 107.64.61(5?), the O1-Mn1-Cl1 bond angle is 113.29(5), the O1A-Mn1-ClA bond angle is 107.17(9), all of which are within normal range of values, where A is the symmetrization operation code 3/2-x, +y, 1-z.

(15) Single crystal X-ray diffraction (XRD) physical phase analysis of Samples 1-Cl.sup.# and 2-Br.sup.# after grinding was performed on a MiniFlex 600 X-ray diffractometer from Rigaku, with a Cu target, a K? radiation source (2=1.54184 ?). The test results are shown in FIG. 1B, one oxidized tris(o-methylphenyl)oxaphosphorus ligand, one semi-occupied Mn.sup.2+ ion and one Br.sup.? ion were contained in the asymmetric unit; by symmetrization operation, it can be seen that Mn is in a tetra-coordinated aberrated tetrahedral geometrical configuration, with a MnBr bond length of 2.4708(5) ? and a MnO bond length of 2.0348(19) ?; centered on Mn, the Br1A-Mn1-Br1 bond angle is 112.82(3), the O1A-Mn1-Br1 bond angle is 106.07(6), the O1A-Mn1-Br1A bond angle is 113.71(6), the O1-Mn1-Br1 bond angle is 113.71(6), and the O1A-Mn1-O1 bond angle is 104.31 (12), all of which are within normal range of values, where A is the symmetrization operation code 1-x, +y, 1/2-z.

(16) Comparison of the theoretical XRD diffraction pattern obtained by fitting X-ray single crystal diffraction with its XRD diffraction pattern measured by X-ray powder diffraction phase analysis is shown in FIGS. 2A-2B, which shows that the XRD diffraction pattern obtained by fitting single-crystal data is in high agreement with its experimentally measured XRD diffraction pattern, which proves that the resulting sample is a high purity and high crystallinity sample.

(17) The X-ray powder diffraction and X-ray single crystal diffraction results show that:

(18) Samples 1-Cl.sup.# (chemical formula C.sub.42H.sub.42Cl.sub.2MnO.sub.2P.sub.2) and 2-Br.sup.# (chemical formula C.sub.42H.sub.42Br.sub.2MnO.sub.2P.sub.2) both belong to a C2/c space group of a monoclinic crystal system.

(19) For Sample 1-Cl.sup.#, the cell parameters are a=21.4929(9) ?, b=10.5149(3) ?, c=18.6578(9) ?, ?=90?, ?=112.674(5?), ?=90?, and Z=4;

(20) For Sample 2-Br.sup.#, the cell parameters are a=18.5888(8) ?, b=10.6170(3) ?, c=21.9189(8) ?, ?=90?, ?=113.149(5?), ?=90?, Z=4.

(21) Test Example 2 Thermal Stability Test Experiment

(22) The thermal stability of Samples 1-Cl.sup.# and 2-Br.sup.# can be measured in a TGA&DSC METTLER TOLEDO thermogravimetric analyzer under nitrogen atmosphere. As shown in FIGS. 3A-3B, Samples 1-Cl.sup.# and 2-Br.sup.# have good thermal stability, and still maintain the structural integrity at 280? C.

(23) Test Example 3 X-Ray Scintillation Performance Test Experiment

(24) X-ray scintillation performance test experiments on Samples 1-Cl.sup.# and 2-Br.sup.# were carried out in the following steps:

(25) A X-ray scintillation performance comprehensive test platform was built by ourselves; before testing the samples, BGO and LYSO purchased from Xiamen Centro Spark Optoelectronics Technology Co., Ltd. were used as reference samples, and the samples had to be screened for photoluminescence performance test under UV excitation before X-ray scintillation performance test, with Edinburgh FLS920 for photoluminescence performance test as selected instrument, in which the excitation source was an Xe lamp, and a specific excitation band of UV could be selected by the filtering system with an excitation slit of 1 mm and a receiving slit of 1 mm.

(26) The experimental spectra of photoluminescence are shown in FIGS. 4A-4B. The optimum photoluminescence peaks of Samples 1-Cl.sup.# and 2-Br.sup.# were at 512?2 nm with green emission under the optimum wavelength excitation at 350 nm.

(27) The experimental spectra of X-ray scintillation properties are shown in FIGS. 5A-5B. The scintillation emission of Samples 1-Cl.sup.# and 2-Br.sup.# was also at 512?2 nm. And when the tube voltage of the X-ray tube was fixed and the tube current of the X-ray tube was changed, both Samples 1-Cl.sup.# and 2-Br.sup.# exhibited scintillation signals at 512?2 nm; the scintillation intensities of Samples 1-Cl.sup.# and 2-Br.sup.# changed linearly with the change of the X-ray dose. When the tube voltage was fixed at 50 kV and the tube current was gradually reduced from 100 ?A to 50 ?A, the X-ray scintillation performance decreased sequentially.

(28) The comparative experimental spectra of the scintillation performance are shown in FIG. 6, in which the tube voltage of the X-ray tube is 50 kV, the tube current of the X-ray tube is 100 ?A, the distance between the sample and the X-ray tube is 5 cm, and the weight of the test sample is 100 mg. It can be seen that, under the same test conditions, the scintillation intensity of Sample 1-Cl.sup.# was determined to be about 0.87 times that of bismuth germanate BGO scintillating crystals, and the scintillation intensity of Sample 2-Br.sup.# was about 4.27 times that of BGO and 0.92 times that of lutetium-yttrium oxyorthosilicate LYSO. Compared with the current commercial scintillating materials, 1-Cl.sup.#?BGO<2-Br.sup.#?LYSO, the scintillating materials described in the present application are comparable in performance to the commercial scintillating materials, yet are much more inexpensive to synthesize, with greatly advantageous conditions.

(29) The experimental detection of X-ray dose is shown in FIG. 7, in which the X-ray dose can be realized by fixing the tube voltage and changing the tube current of the X-ray tube, and the dose detected by the reagent is corrected by a RAMION radiation dosimeter. The linear slope of the curve indicates the detection sensitivity of the scintillating material to high-energy X-rays, |k(2-Br)|>|k(1-Cl), which indicates that the detection sensitivity of the scintillating material Sample 2-Br.sup.# to high-energy X-rays is better than that of the scintillating material Sample 1-Cl.sup.#. According to the International Union of Pure and Applied Chemistry, the dose detection limit of X-rays is 3?, ? is the ratio of the standard deviation of the instrumental noise to the slope of the X-ray dose detection curve |k|, and the standard deviation of the instrumental noise is 0.97, so the detection limits of Samples 1-Cl.sup.# and 2-Br.sup.# can be derived to be 3.90 ?Gy.sub.air/s and 0.82 ?Gy.sub.air/S, respectively, which are below the conventional medical diagnostic dose criterion of 5.50 ?Gy.sub.air/s. This indicates that Sample 1-Cl.sup.# and Sample 2-Br.sup.# have sensitive X-ray detection capability.

(30) The above Examples are merely some of the Examples of the present application, and do not limit the present application in any form. Although the present application is disclosed above with the preferred Examples, the present application is not limited thereto. Some changes or modifications made by any technical personnel familiar with the profession using the technical content disclosed above without departing from the scope of the technical solutions of the present application are equivalent to equivalent implementation cases and fall within the scope of the technical solutions.