A terbium-based metal organic framework crystal material, a preparation method and application thereof
By synthesizing terbium-based metal-organic framework crystal materials using a microwave-assisted method, the problems of poor selectivity of fluorescent materials and long processing time of traditional solvothermal methods in existing technologies have been solved, enabling highly specific fluorescence detection of tetracycline hydrochloride and low-cost large-scale production.
Patent Information
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- HENAN ACAD OF SCI CARBON MATRIX COMPOSITES RES INST
- Filing Date
- 2026-04-28
- Publication Date
- 2026-06-23
AI Technical Summary
Existing fluorescent materials are difficult to achieve a highly specific response to tetracycline hydrochloride, and the traditional solvothermal synthesis of rare earth metal-organic framework materials is time-consuming and costly, which cannot meet the needs of large-scale industrial production.
Terbium-based metal-organic framework crystal materials were synthesized using a microwave-assisted method. The reaction of 5-((4-(1H-1,2,4-triazol-1-yl)benzyl)oxy)isophthalic acid with terbium trichloride hexahydrate in a mixed solvent formed the [Tb2(trzbi)2(NO3)2(H2O)]n structure. Highly crystalline terbium-based metal-organic framework crystal materials were then prepared using a combination of solvothermal and microwave-assisted methods.
It achieves highly specific fluorescence detection of tetracycline hydrochloride, with fast response, good selectivity, shortened synthesis time, reduced production costs, and is suitable for large-scale production.
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Figure CN122255502A_ABST
Abstract
Description
Technical Field
[0001] This invention belongs to the field of metal-organic framework materials and analytical testing technology, specifically relating to a terbium-based metal-organic framework crystal material, its preparation method, and its application. Background Technology
[0002] Tetracycline hydrochloride is a broad-spectrum antibiotic widely used in clinical anti-infective treatment, livestock farming, and aquaculture. Overuse can lead to tetracycline residues in food, the environment, and organisms, causing problems such as intestinal flora imbalance, allergic reactions, and bacterial resistance, as well as environmental pollution. Therefore, developing a rapid and accurate method for detecting tetracycline hydrochloride is crucial for monitoring and controlling its dosage in food, environmental, and biological samples.
[0003] Currently, there are a series of typical methods for the detection and analysis of tetracycline hydrochloride, including high-performance liquid chromatography (HPLC), mass spectrometry (MS), enzyme-linked immunosorbent assay (ELISA), and electrochemical analysis. However, most of these methods involve complex operating procedures, slow response times, and high costs, and some exhibit poor selectivity. In contrast, fluorescent probes offer advantages such as simple and convenient operation, fast response speed, and high sensitivity, making them a promising method for tetracycline hydrochloride detection. Furthermore, existing fluorescent materials struggle to achieve highly specific responses to tetracycline hydrochloride; therefore, there is an urgent need to develop novel fluorescent materials to achieve specific fluorescent detection of tetracycline hydrochloride.
[0004] Metal-organic frameworks (MOFs) exhibit great potential in fluorescence sensing due to their unique structural characteristics, such as high specific surface area, tunable pore size, and abundant metal active sites. Among them, rare-earth MOFs with tunable multi-luminescent centers possess excellent properties such as long fluorescence lifetime, large Stokes shift, sharp linear emission bands, and good spectral monochromaticity. Therefore, constructing MOFs using terbium and organic ligands holds promise for developing highly sensitive and selective fluorescence sensors for the detection of tetracycline hydrochloride.
[0005] However, traditional solvothermal methods have significant limitations in synthesizing such rare-earth metal-organic framework materials. Solvothermal methods require prolonged reactions at high temperatures, typically lasting several hours or even days. These prolonged high-temperature reactions not only consume substantial amounts of energy, increasing production costs, but also result in low reaction efficiency, failing to meet the demands of large-scale industrial production for efficient and low-cost material preparation. This invention further proposes a microwave-assisted synthesis method, shortening the reaction time to 0.5-4 hours, significantly improving efficiency, and providing a new approach for large-scale production. Summary of the Invention
[0006] To address the aforementioned technical problems, this invention provides a terbium-based metal-organic framework crystal material, its preparation method, and its applications.
[0007] This invention employs two efficient preparation methods (solvothermal method and microwave-assisted method) and their application in the fluorescence detection of tetracycline hydrochloride. The terbium-based metal-organic framework crystal material prepared by this invention exhibits high crystallinity, stable luminescence intensity under aqueous solutions at different pH values, and specific fluorescence response.
[0008] The terbium-based metal-organic framework crystal material of the present invention is formed by coordinating 5-((4-(1H-1,2,4-triazol-1-yl)benzyl)oxy)isophthalic acid organic ligand with terbium trichloride hexahydrate.
[0009] The structure of the 5-((4-(1H-1,2,4-triazol-1-yl)benzyl)oxy)isophthalic acid organic ligand (H2trzbi) of this invention is as follows:
[0010] ;
[0011] Furthermore, the chemical formula of the terbium-based metal-organic framework crystal material is [Tb2(trzbi)2(NO3)2(H2O)]. n , where trzbi is the ligand of H2trzbi after deprotonation; the terbium-based metal-organic framework crystal material belongs to the monoclinic crystal system, space group P21 / n, with unit cell parameters a=8.5269(8)Å, b=23.217(3)Å, c=19.116(7)Å, α=90°, β=95.631(3)°, γ=90°.
[0012] Furthermore, the asymmetric structural unit of terbium-based metal-organic framework crystal materials consists of two independent Tb 3+ Ions, two dehydrogenated trzbi 2- Ligands, two coordinated NOs 3- It consists of a coordinated H2O molecule; two adjacent Tb 3+ The ions are linked by ligand carboxyl groups and coordinated nitrate ions to form a binuclear secondary structural unit [Tb2(COO)2(NO3)2], which is connected by ligands to form a three-dimensional framework.
[0013] This invention provides two methods for preparing terbium-based metal-organic framework crystal materials:
[0014] Solvothermal method: 5-((4-(1H-1,2,4-triazol-1-yl)benzyl)oxy)isophthalic acid (H2trzbi) and terbium trichloride hexahydrate were dissolved in a mixed solvent of acetonitrile, water and nitric acid to obtain a mixed solution; the mixed solution was transferred to a polytetrafluoroethylene reactor for hydrothermal reaction, and after the reaction was completed, it was naturally cooled to room temperature, filtered and washed to obtain terbium-based metal-organic framework crystal material.
[0015] Microwave-assisted method: 5-((4-(1H-1,2,4-triazol-1-yl)benzyl)oxy)isophthalic acid (H2trzbi) and terbium trichloride hexahydrate were dissolved in a mixed solvent of acetonitrile, water and nitric acid, and then transferred to a microwave reaction vessel. The mixture was heated to a certain time under the set microwave heating power. After the reaction was completed, the mixture was allowed to cool naturally to room temperature, filtered and washed to obtain terbium-based metal-organic framework crystal materials.
[0016] Application of terbium-based metal-organic framework crystal materials in the fluorescence detection of tetracycline hydrochloride.
[0017] Advantages of this invention:
[0018] I. This invention synthesizes terbium-based metal-organic framework crystal materials, exhibiting a novel three-dimensional framework;
[0019] II. The terbium-based metal-organic framework crystal material prepared by the one-pot solvothermal method of this invention has a cubic shape and high crystallinity; the synthesis method is simple to operate, low in cost, and can be mass-produced.
[0020] Third, the terbium-based metal-organic framework crystal material prepared by this invention has stable luminescence intensity in aqueous solutions with a wide pH range, and can specifically detect tetracycline hydrochloride. It has the characteristics of high sensitivity, fast response and good selectivity, with a detection limit of 0.13 μM. Attached Figure Description
[0021] Figure 1 These are microscopic morphology images of the terbium-based metal-organic framework crystal material prepared in Example 1;
[0022] Figure 2 This is a diagram of the asymmetric structural unit of the terbium-based metal-organic framework crystal material prepared in Example 1;
[0023] Figure 3 This is a three-dimensional structural diagram of the terbium-based metal-organic framework crystal material prepared in Example 1;
[0024] Figure 4 This is the powder PXRD pattern of the terbium-based metal-organic framework crystal material prepared in Example 1;
[0025] Figure 5The luminescence intensity of the terbium-based metal-organic framework crystal material prepared in Example 1 under different pH aqueous solutions;
[0026] Figure 6 The fluorescence spectra of tetracycline hydrochloride solutions of different concentrations containing the terbium-based metal-organic framework crystal material prepared in Example 1 are shown.
[0027] Figure 7 It is a standard curve of (I0 / I-1) versus the concentration of tetracycline hydrochloride solution. Detailed Implementation
[0028] Specific Implementation Method 1: This implementation method relates to a terbium-based metal-organic framework crystal material with the chemical formula [Tb₂(trzbi)₂(NO₃)₂(H₂O)]. n , where trzbi is the ligand of H2trzbi after deprotonation; the terbium-based metal-organic framework crystal material belongs to the monoclinic crystal system, space group P21 / n, with unit cell parameters a=8.5269(8)Å, b=23.217(3)Å, c=19.116(7)Å, α=90°, β=95.631(3)°, γ=90°.
[0029] The terbium-based metal-organic framework crystal material described in this embodiment exhibits stable luminescence intensity in aqueous solutions with different pH values, enabling highly specific fluorescence detection of tetracycline hydrochloride.
[0030] Specific Implementation Method Two: This implementation method differs from Specific Implementation Method One in that the asymmetric structural unit of the terbium-based metal-organic framework crystal material consists of two independent Tb 3+ Ions, two dehydrogenated trzbi 2- Ligands, two coordinated NOs 3- It consists of a coordinated H2O molecule; two adjacent Tb 3+ The ions are linked by ligand carboxyl groups and coordinated nitrate ions to form a [Tb2(COO)2(NO3)2] binuclear secondary structural unit, which is then connected by ligands to form a three-dimensional framework. Other steps are the same as in Specific Implementation Method 1.
[0031] Specific Implementation Method 3: This implementation method is a preparation method for terbium-based metal-organic framework crystal materials. The preparation method is a solvothermal method, specifically completed according to the following steps:
[0032] 5-((4-(1H-1,2,4-triazol-1-yl)benzyl)oxy)isophthalic acid and terbium trichloride hexahydrate were dissolved in a mixed solvent of acetonitrile, water and nitric acid to obtain a mixed solution. The mixed solution was transferred to a polytetrafluoroethylene reactor for hydrothermal reaction. After the reaction was completed, the mixture was naturally cooled to room temperature, filtered and washed to obtain a terbium-based metal-organic framework crystal material.
[0033] Specific Implementation Method Four: This implementation method is a method for preparing terbium-based metal-organic framework crystal materials. The preparation method is a microwave-assisted method, specifically completed according to the following steps:
[0034] 5-((4-(1H-1,2,4-triazol-1-yl)benzyl)oxy)isophthalic acid and terbium trichloride hexahydrate were dissolved in a mixed solvent of acetonitrile, water and nitric acid, and then transferred to a microwave reaction vessel. The mixture was heated to a certain time under the set microwave heating power. After the reaction was completed, the mixture was allowed to cool to room temperature, filtered and washed to obtain terbium-based metal-organic framework crystal material.
[0035] Specific Implementation Method Five: This implementation method differs from Specific Implementation Methods One to Four in that: the molar ratio of 5-((4-(1H-1,2,4-triazol-1-yl)benzyl)oxy)isophthalic acid and terbium trichloride hexahydrate is 0.1:(0.1~0.2); the 5-((4-(1H-1,2,4-triazol-1-yl)benzyl)oxy)isophthalic acid is a commercially available product, purchased from Jinan Henghua Technology Co., Ltd. The other steps are the same as in Specific Implementation Methods One to Four.
[0036] Specific Implementation Method Six: This implementation method differs from Specific Implementation Methods One to Five in that: the mixed solvent of acetonitrile, water, and nitric acid is composed of acetonitrile, deionized water, and nitric acid with a concentration of 0.5 mol / L; the volume ratio of acetonitrile, deionized water, and nitric acid with a concentration of 0.5 mol / L is 4:(1.5~2.5):(0.5~1); the amount of 5-((4-(1H-1,2,4-triazol-1-yl)benzyl)oxy)isophthalic acid to the volume ratio of the mixed solvent of acetonitrile, water, and nitric acid is 0.1 mmol:(6 mL~7 mL); the terbium-based metal-organic framework crystal material is cubic in shape with a length of approximately 150 μm. Other steps are the same as in Specific Implementation Methods One to Five.
[0037] Specific Implementation Method Seven: This implementation method differs from Specific Implementation Methods One to Six in that the hydrothermal reaction temperature is 120℃~180℃, and the hydrothermal reaction time is 72h~96h. Other steps are the same as in Specific Implementation Methods One to Six.
[0038] Specific Implementation Method Eight: The difference between this implementation method and Specific Implementation Methods One to Seven is that the heating reaction is carried out at a microwave heating power of 200W to 500W for 0.5h to 4h, and the heating reaction temperature is 100℃ to 130℃.
[0039] The other steps are the same as those in Specific Implementation Methods 1 to 7.
[0040] Specific Implementation Method Nine: This implementation method differs from Specific Implementation Methods One to Eight in that the terbium-based metal-organic framework crystal material is used in the fluorescence detection of tetracycline hydrochloride. The other steps are the same as in Specific Implementation Methods One to Eight.
[0041] Specific Implementation Method Ten: This implementation method differs from Specific Implementation Methods One through Nine in that: the method for quantitatively detecting the concentration of tetracycline hydrochloride in the test solution using terbium-based metal-organic framework crystal materials is specifically completed according to the following steps:
[0042] I. Plotting the standard curve:
[0043] Five mg of terbium-based metal-organic framework crystal material was dispersed in 5 mL of tetracycline hydrochloride solutions with pH 7 and concentrations of 5 μM, 10 μM, 15 μM, 20 μM, 25 μM, 30 μM, 45 μM, 60 μM, 75 μM, 90 μM, 120 μM, 150 μM, 180 μM, 210 μM, and 240 μM, respectively. The solutions were excited with light from 310 nm to 330 nm, and the fluorescence intensity I at 545 nm was detected. Five mg of terbium-based metal-organic framework crystal material was also dispersed in 5 mL of deionized water and excited with light from 310 nm to 330 nm; the fluorescence intensity I0 at 545 nm was detected. A standard curve was obtained by fitting the concentration of the tetracycline hydrochloride solution to the x-axis and (I0 / I-1) to the y-axis.
[0044] 2. Calculate the concentration of tetracycline hydrochloride in the test solution using a standard curve. Other steps are the same as in Specific Implementation Methods 1 to 9.
[0045] The present invention will be further described below with reference to the embodiments, but the present invention is not limited to the following embodiments:
[0046] Unless otherwise specified, "room temperature" in this invention refers to 20-30°C. Unless otherwise specified, all reagents and materials used are commercially available and have not undergone further purification.
[0047] Example 1: A method for preparing terbium-based metal-organic framework crystal materials using a solvothermal method, specifically comprising the following steps:
[0048] 0.1 mmol of 5-((4-(1H-1,2,4-triazol-1-yl)benzyl)oxy)isophthalic acid and 0.1 mmol of terbium trichloride hexahydrate were dissolved in 7 mL of a mixed solvent of acetonitrile, water, and 0.5 mol / L nitric acid (volume ratio of acetonitrile, water, and 0.5 mol / L nitric acid was 4:2:1). The solution was stirred at room temperature for 30 min to obtain a mixed solution. The mixed solution was transferred to a 25 mL polytetrafluoroethylene reactor and hydrothermally reacted at 160 °C for 96 h. After the reaction was completed, the mixture was naturally cooled to room temperature, and colorless, transparent blocky crystals were collected. The crystals were washed three times each with deionized water and anhydrous ethanol, and finally dried in air to obtain terbium-based metal-organic framework crystal material ([Tb2(trzbi)2(NO3)2(H2O)). n ).
[0049] Example 2: A method for preparing terbium-based metal-organic framework crystal materials using a microwave-assisted method, specifically comprising the following steps:
[0050] 0.1 mmol of 5-((4-(1H-1,2,4-triazol-1-yl)benzyl)oxy)isophthalic acid and 0.1 mmol of terbium trichloride hexahydrate were dissolved in 7 mL of a mixed solvent of acetonitrile, water, and 0.5 mol / L nitric acid (volume ratio of acetonitrile, water, and 0.5 mol / L nitric acid was 4:2:1). The mixture was stirred at room temperature for 30 min to obtain a mixed solution. The mixed solution was transferred to a microwave reaction vessel and heated at 300 W for 2 h at a temperature of 120 °C. After the reaction was completed, the mixture was allowed to cool naturally to room temperature. Colorless and transparent bulk crystals were collected and washed three times each with deionized water and anhydrous ethanol, respectively. Finally, the crystals were dried in air to obtain terbium-based metal-organic framework crystal material ([Tb2(trzbi)2(NO3)2(H2O)). n ).
[0051] Figure 1 These are microscopic morphology images of the terbium-based metal-organic framework crystal material prepared in Example 1;
[0052] from Figure 1 It can be seen that the terbium-based metal-organic framework crystal material prepared in Example 1 is cubic in shape and has a length of about 150 μm.
[0053] The terbium-based metal-organic framework crystal material prepared in Example 1 was subjected to X-ray single-crystal diffraction analysis to collect diffraction data, which was then analyzed using Shelxt software.
[0054] Depend on Figure 2 It can be seen that the asymmetric structural unit of the terbium-based metal-organic framework crystal material prepared in Example 1 contains two independent Tb 3+ Ions, two trzbi undergoing dehydrogenation2- Ligands, two NO molecules in a coordinated state 3- And a coordinated H2O molecule.
[0055] Figure 3 This is a three-dimensional structural diagram of the terbium-based metal-organic framework crystal material prepared in Example 1;
[0056] Depend on Figure 3 It can be seen that: the central metal Tb 3+ The ions form a three-dimensional framework structure by connecting the carboxyl oxygen atom in the 5-((4-(1H-1,2,4-triazol-1-yl)benzyl)oxy)isophthalic acid ligand with the nitrogen atom on the five-membered ring.
[0057] The terbium-based metal-organic framework crystal material prepared in Example 1 was characterized by XRD. The characterization results are shown in the figure. Figure 4 ;
[0058] Figure 4 This is the powder PXRD pattern of the terbium-based metal-organic framework crystal material prepared in Example 1;
[0059] from Figure 4 It can be seen that it has reliable phase purity, which provides a guarantee for its fluorescence sensing application.
[0060] The fluorescence stability of the terbium-based metal-organic framework crystal material prepared in Example 1 was characterized by measuring the fluorescence intensity at different pH aqueous solutions. The relevant results can be found in [link to relevant documentation]. Figure 5 .
[0061] Figure 5 The luminescence intensity of the terbium-based metal-organic framework crystal material prepared in Example 1 under different pH aqueous solutions;
[0062] Figure 5 The luminescence intensity of the terbium-based metal-organic framework crystal material prepared in Example 1 is shown in aqueous solutions with different pH values. The results show that the luminescence intensity of the material is stable over a wide pH range and has good resistance to pH interference.
[0063] Crystallographic data of the terbium-based metal-organic framework crystal material prepared in Example 1 are shown in Table 1.
[0064] Table 1 Crystallographic data
[0065]
[0066] Application Example 1:
[0067] 5 mg of the terbium-based metal-organic framework crystal material prepared in Example 1 was dispersed into 5 mL of tetracycline hydrochloride solutions with pH 7 and concentrations of 5 μM, 10 μM, 15 μM, 20 μM, 25 μM, 30 μM, 45 μM, 60 μM, 75 μM, 90 μM, 120 μM, 150 μM, 180 μM, 210 μM, and 240 μM, respectively. The solutions were excited with light at 310 nm to 330 nm, and the fluorescence spectrum at 400 nm to 700 nm was detected. The fluorescence intensity I at 545 nm was also detected. 5 mg of the terbium prepared in Example 1 was then... The metal-organic framework crystal material was dispersed in 5 mL of deionized water and excited with excitation light at 310 nm to 330 nm. The fluorescence spectrum at 400 nm to 700 nm was detected. The fluorescence intensity I0 at 545 nm was detected. A standard curve was obtained by fitting the concentration of tetracycline hydrochloride solution as the abscissa and (I0 / I-1) as the ordinate. The detection limit for tetracycline was found to be 0.13 μM by quantitative analysis according to the Stern-Volmer (SV) equation.
[0068] Figure 6 The fluorescence spectra of tetracycline hydrochloride solutions of different concentrations containing the terbium-based metal-organic framework crystal material prepared in Example 1 are shown.
[0069] from Figure 6 It can be seen that as the concentration of tetracycline hydrochloride increases, the characteristic fluorescence emission peak of terbium-based metal-organic framework materials gradually weakens.
[0070] Figure 7 It is a standard curve of (I0 / I-1) versus the concentration of tetracycline hydrochloride solution;
[0071] from Figure 7 It can be seen that the terbium-based metal-organic framework crystal material prepared in Example 1 exhibits a good linear relationship with tetracycline hydrochloride concentrations. This indicates that the terbium-based metal-organic framework material of the present invention can achieve fluorescence detection of tetracycline hydrochloride.
Claims
1. A terbium-based metal-organic framework crystal material, characterized in that, The chemical formula of the terbium-based metal-organic framework crystal material is [Tb2(trzbi)2(NO3)2(H2O)]. n , where trzbi is the ligand of H2trzbi after deprotonation; the terbium-based metal-organic framework crystal material belongs to the monoclinic crystal system, space group P21 / n, with unit cell parameters a=8.5269(8)Å, b=23.217(3)Å, c=19.116(7)Å, α=90°, β=95.631(3)°, γ=90°.
2. The terbium-based metal-organic framework crystal material according to claim 1, characterized in that, The asymmetric structural unit of the terbium-based metal-organic framework crystal material consists of two independent Tb 3+ Ions, two dehydrogenated trzbi 2- Ligands, two coordinated NOs 3- It consists of a coordinated H2O molecule; two adjacent Tb 3+ The ions are linked by ligand carboxyl groups and coordinated nitrate ions to form a binuclear secondary structural unit [Tb2(COO)2(NO3)2], which is connected by ligands to form a three-dimensional framework.
3. The method for preparing a terbium-based metal-organic framework crystal material as described in claim 1, characterized in that, The preparation method is a solvothermal method, specifically carried out according to the following steps: 5-((4-(1H-1,2,4-triazol-1-yl)benzyl)oxy)isophthalic acid and terbium trichloride hexahydrate were dissolved in a mixed solvent of acetonitrile, water and nitric acid to obtain a mixed solution. The mixed solution was transferred to a polytetrafluoroethylene reactor for hydrothermal reaction. After the reaction was completed, the mixture was naturally cooled to room temperature, filtered and washed to obtain a terbium-based metal-organic framework crystal material.
4. The method for preparing a terbium-based metal-organic framework crystal material as described in claim 1, characterized in that, The preparation method is a microwave-assisted method, specifically carried out according to the following steps: 5-((4-(1H-1,2,4-triazol-1-yl)benzyl)oxy)isophthalic acid and terbium trichloride hexahydrate were dissolved in a mixed solvent of acetonitrile, water and nitric acid, and then transferred to a microwave reaction vessel. The mixture was heated to a certain time under the set microwave heating power. After the reaction was completed, the mixture was allowed to cool to room temperature, filtered and washed to obtain terbium-based metal-organic framework crystal material.
5. A method for preparing a terbium-based metal-organic framework crystal material according to claim 3 or 4, characterized in that, The molar ratio of 5-((4-(1H-1,2,4-triazol-1-yl)benzyl)oxy)isophthalic acid to terbium trichloride hexahydrate is 0.1:(0.1~0.2); the 5-((4-(1H-1,2,4-triazol-1-yl)benzyl)oxy)isophthalic acid is a commercially available product, purchased from Jinan Henghua Technology Co., Ltd.
6. A method for preparing a terbium-based metal-organic framework crystal material according to claim 3 or 4, characterized in that, The mixed solvent of acetonitrile, water, and nitric acid consists of acetonitrile, deionized water, and nitric acid with a concentration of 0.5 mol / L; the volume ratio of acetonitrile, deionized water, and nitric acid with a concentration of 0.5 mol / L is 4:(1.5~2.5):(0.5~1); the molar amount of 5-((4-(1H-1,2,4-triazol-1-yl)benzyl)oxy)isophthalic acid to the volume ratio of the mixed solvent of acetonitrile, water, and nitric acid is 0.1 mmol:(6 mL~7 mL); the terbium-based metal-organic framework crystal material is cubic in shape and approximately 150 μm in length.
7. The method for preparing a terbium-based metal-organic framework crystal material according to claim 3, characterized in that, The hydrothermal reaction temperature is 120℃~180℃, and the hydrothermal reaction time is 72h~96h.
8. The method for preparing a terbium-based metal-organic framework crystal material according to claim 4, characterized in that, The reaction was heated for 0.5 to 4 hours at a microwave heating power of 200W to 500W, and the temperature of the reaction was 100℃ to 130℃.
9. The application of the terbium-based metal-organic framework crystal material as described in claim 1, characterized in that, The terbium-based metal-organic framework crystal material is used in the fluorescence detection of tetracycline hydrochloride.
10. The application of a terbium-based metal-organic framework crystal material according to claim 9, characterized in that, The method for quantitatively detecting the concentration of tetracycline hydrochloride in a test solution using terbium-based metal-organic framework crystal materials is specifically carried out according to the following steps: I. Plotting the standard curve: Five mg of terbium-based metal-organic framework crystal material was dispersed in 5 mL of tetracycline hydrochloride solutions with pH 7 and concentrations of 5 μM, 10 μM, 15 μM, 20 μM, 25 μM, 30 μM, 45 μM, 60 μM, 75 μM, 90 μM, 120 μM, 150 μM, 180 μM, 210 μM, and 240 μM, respectively. The solutions were excited with light from 310 nm to 330 nm, and the fluorescence intensity I at 545 nm was detected. Five mg of terbium-based metal-organic framework crystal material was also dispersed in 5 mL of deionized water and excited with light from 310 nm to 330 nm; the fluorescence intensity I0 at 545 nm was detected. The standard curve was obtained by fitting the concentration of tetracycline hydrochloride solution to the x-axis and (I0 / I-1) to the y-axis.
2. Calculate the concentration of tetracycline hydrochloride in the test solution using the standard curve.