Zinc (II) metal organic framework material for Cu < 2 + > and NB detection and organic dye photocatalytic degradation and preparation method thereof
By preparing the zinc(II) metal-organic framework material [Zn(cpt)2]n, the problems of high-sensitivity detection of Cu2+ and NB and photocatalytic degradation of organic dyes were solved, achieving simple and efficient detection and degradation effects.
Patent Information
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- SHAANXI SCI TECH UNIV
- Filing Date
- 2026-01-27
- Publication Date
- 2026-05-12
AI Technical Summary
Existing technologies are difficult to detect Cu2+ and NB quickly, easily, and with high sensitivity, and are also difficult to effectively degrade organic dyes. Traditional methods are cumbersome to operate, costly, and difficult to conduct on-site testing.
A zinc(II) metal-organic framework material [Zn(cpt)2]n was prepared by a one-pot hydrothermal reaction. Cu2+ and NB were detected by fluorescence sensing, and its photocatalytic properties were used to degrade the organic dye Rhodamine B.
It achieves highly selective and sensitive fluorescence detection of Cu2+ and NB, and exhibits good photocatalytic degradation effect on Rhodamine B. The preparation method is simple, has high yield, and good reproducibility.
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Abstract
Description
Technical Field
[0001] This invention relates to the field of fluorescence sensing technology, and more particularly to a method for Cu 2+ Zinc(II) metal-organic framework materials and their preparation methods for NB detection and photocatalytic degradation of organic dyes. Background Technology
[0002] With rapid industrialization, the combined pollution of water bodies by heavy metals and organic pollutants poses a serious threat to the ecological environment and human health. Among these, copper ions (Cu...) 2+ These pollutants can accumulate in the human body through the food chain, and excessive intake can lead to liver and kidney damage and neurotoxicity. Nitrobenzene (NB), as a typical industrial toxin, carries carcinogenic and mutagenic risks. Similarly, the emission of various organic dye pollutants poses another major threat to ecosystems and human health. These pollutants are chemically stable, persistent, and difficult to degrade naturally, making them particularly difficult to treat.
[0003] Currently, for Cu 2+ Conventional detection techniques for targets such as trace elements (NB) rely heavily on large instruments, which are cumbersome to operate, costly, and difficult to implement rapidly on-site. Therefore, developing novel detection methods that are highly sensitive, selective, fast-responding, and easy to operate is of great practical significance. In recent years, metal-organic frameworks (MOFs) have become a research hotspot in the field of fluorescence sensing due to their tunable structure and excellent luminescence properties. MOF-based fluorescent probes can achieve highly selective identification of targets through specific changes in luminescence intensity, offering significant advantages such as low cost, fast response, and ease of visualization monitoring, providing a new solution for trace environmental detection.
[0004] Photocatalysis is a green and efficient method for treating recalcitrant organic pollutants. In particular, the use of transition metal-based metal-organic frameworks (MOFs) as photocatalysts demonstrates significant potential for enhancing light absorption and promoting reactive oxygen species (ROS) generation due to their unique structure and electronic properties. Under light irradiation, these catalysts are activated to produce ROS, thereby breaking down complex dye molecules into simpler, less harmful compounds, providing an effective pathway for the purification of organic pollutants. The integration of fluorescence sensing with photocatalytic systems allows a single material to both detect and degrade organic pollutants. This innovative strategy has greatly promoted the development of sustainable water treatment technologies. Summary of the Invention
[0005] The technical problem to be solved by the present invention is to address the shortcomings of the prior art by providing a method for Cu 2+Zinc(II) metal-organic framework materials for NB detection and photocatalytic degradation of organic dyes and their preparation methods are disclosed. The preparation method has advantages such as mild conditions, simple operation, high yield, and good reproducibility. The prepared zinc(II) metal-organic framework materials exhibit good structural stability and fluorescence properties, and their ability to detect Cu... 2+ Both NB and NB have high selectivity and sensitivity, making them suitable for detecting Cu. 2+ It is a good fluorescence sensor for NB; it also has good photocatalytic degradation performance of organic fuels, and has a good photocatalytic degradation effect on the organic dye Rhodamine B.
[0006] This invention provides a zinc(II) metal-organic framework material, the chemical formula of which is [Zn(cpt)2]. n The single-crystal molecular formula of the zinc(II) metal-organic framework material is C0. 56 H 36 ZnN6O6.
[0007] According to the zinc(II) metal-organic framework material provided by the present invention, the ligand (cpt) in the chemical formula of the zinc(II) metal-organic framework material... - The Hcpt is a deprotonated Hcpt, wherein the Hcpt is 4′-(4-(4-carboxyphenoxy)phenyl)-4,2′:6′,4″-terpyridine;
[0008] The structural formula of Hcpt is: .
[0009] According to the zinc(II) metal-organic framework material provided by the present invention, the zinc(II) metal-organic framework material is monoclinic with space group C2 / c and cell parameters including a=12.24424(19) Å, b=6.38823(7) Å, c=31.6860(4) Å, α=90°Å, β=100.5124(14)°Å and γ=90°Å.
[0010] This invention provides a method for preparing the above-mentioned zinc(II) metal-organic framework material, comprising the following steps:
[0011] S1. Take distilled water and acetonitrile to obtain a mixed solution. Dissolve Hcpt and divalent zinc metal salt in the mixed solution. Stir at room temperature to react fully to obtain an intermediate product. Transfer the intermediate product to a reaction vessel and react at a constant temperature to obtain the reaction product.
[0012] S2. After the reaction product is cooled to room temperature, it is cooled and crystallized. After washing and drying, zinc(II) metal-organic framework material is obtained.
[0013] According to the preparation method provided by the present invention, the divalent zinc metal salt in S1 is Zn(NO3)2, the stirring reaction time is 30 min, the lining of the reaction vessel is polytetrafluoroethylene, the heating rate of the reaction vessel is 5 °C / h, the temperature of the constant temperature reaction is 160 °C, and the constant temperature reaction time is 72 h.
[0014] According to the preparation method provided by the present invention, the volume ratio of distilled water to acetonitrile in the mixed solution in S1 is 2:1, and the volume ratio of Hcpt, divalent zinc metal salt and mixed solution is 0.05-0.1 mmol: 0.05-0.1 mmol: 9 mL.
[0015] According to the preparation method provided by the present invention, the cooling rate in S2 is 5 °C / h, the washing detergent is anhydrous ethanol, the drying temperature is 60 °C, and the drying time is 3 h.
[0016] This invention also provides an application of the above-mentioned zinc(II) metal-organic framework material, wherein the zinc(II) metal-organic framework material is used for fluorescence detection of Cu. 2+ And NB, for Cu 2+ Both NB and NB exhibit high sensitivity and selectivity, and can photocatalytically degrade Rhodamine B.
[0017] Compared with the prior art, the present invention has the following advantages:
[0018] (1) The present invention uses a one-pot hydrothermal reaction to prepare zinc(II) metal-organic framework materials. The chemical formula of the zinc(II) metal-organic framework material is [Zn(cpt)2]. n Its molecular formula is C 56 H 36 The preparation method of ZnN6O6 has the advantages of simple process, convenient operation, high yield and good reproducibility.
[0019] (2) The zinc(II) metal-organic framework material prepared by this invention has good fluorescence properties and is effective against Cu. 2+ Both NB and NB exhibit high selectivity and high sensitivity, and can effectively detect Cu through fluorescence quenching. 2+ And NB. Furthermore, the metal-organic framework material prepared by this invention also exhibits excellent photocatalytic performance, demonstrating a good photocatalytic degradation effect on the organic dye Rhodamine B. Attached Figure Description
[0020] Figure 1 This is a coordination environment diagram of Zn(II) metal-organic framework materials;
[0021] Figure 2 This is a one-dimensional structural diagram of zinc(II) metal-organic framework materials;
[0022] Figure 3 This is a two-dimensional network structure diagram of zinc(II) metal-organic framework materials;
[0023] Figure 4 This is a topological diagram of zinc(II) metal-organic framework materials;
[0024] Figure 5 This is a three-dimensional supramolecular structure diagram of zinc(II) metal-organic framework materials;
[0025] Figure 6 This is the PXRD pattern of zinc(II) metal-organic framework materials;
[0026] Figure 7 This is the fluorescence emission spectrum of the zinc(II) metal-organic framework material and the ligand Hcpt;
[0027] Figure 8 These are fluorescence emission spectra of zinc(II) metal-organic framework materials in different ions;
[0028] Figure 9 Zinc(II) metal-organic framework materials in different Cu 2+ Fluorescence emission spectrum at concentration;
[0029] Figure 10 This is a Stern–Volmer curve of zinc(II) metal-organic framework materials for different ions;
[0030] Figure 11 These are fluorescence emission spectra of zinc(II) metal-organic framework materials for detecting different small molecule compounds;
[0031] Figure 12 This is a graph showing the degradation rate of RhB by zinc(II) metal-organic framework materials;
[0032] Figure 13 It is a zinc(II) metal-organic framework material for DMPO- . OH - EPR spectrum;
[0033] Figure 14 It is a zinc(II) metal-organic framework material for DMPO- . O2 - The EPR spectrum. Detailed Implementation
[0034] Example 1
[0035] This embodiment provides a method for preparing a zinc(II) metal-organic framework material, the specific steps of which are as follows:
[0036] S1. A mixed solution was prepared by mixing distilled water and acetonitrile at a volume ratio of 2:1. 0.05 mmol of the ligand 4′-(4-(4-carboxyphenoxy)phenyl)-4,2′:6′,4″-terpyridine (Hcpt) and 0.1 mmol of the metal salt Zn(NO3)2 were dissolved in 9 mL of the mixed solution. After stirring at room temperature for 30 min to allow the reaction to proceed, an intermediate product was obtained. The intermediate product was transferred to a high-pressure reactor lined with polytetrafluoroethylene. The temperature inside the high-pressure reactor was increased to 160℃ at a rate of 5℃ / h, and a solvothermal reaction was carried out for 3 days to obtain the reaction product.
[0037] The structural formula for Hcpt is: ;
[0038] S2. The reaction product obtained in S1 is cooled and crystallized at a rate of 5 °C / h. After washing with anhydrous ethanol and filtering under reduced pressure, a crystalline powder is obtained. This powder is then dried in an oven at 60 °C for 3 hours to obtain zinc(II) metal-organic framework material 1, namely [Zn(cpt)2]. n The yield was 63.71%.
[0039] Example 2
[0040] S1. A mixed solution was prepared by mixing distilled water and acetonitrile at a volume ratio of 2:1. 0.1 mmol of ligand Hcpt and 0.05 mmol of metal salt Zn(NO3)2 were dissolved in 9 mL of the mixed solution. After stirring at room temperature for 30 min to allow the reaction to proceed, an intermediate product was obtained. The intermediate product was transferred to a high-pressure reactor lined with polytetrafluoroethylene. The temperature inside the high-pressure reactor was increased to 160 °C at a heating rate of 5 °C / h. The solvothermal reaction was carried out for 3 days to obtain the reaction product.
[0041] S2. The reaction product obtained in S1 is cooled and crystallized at a rate of 5 °C / h. After washing with anhydrous ethanol and filtering under reduced pressure, crystalline powder is obtained. This powder is then dried in an oven at 60 °C for 3 h to obtain zinc(II) metal-organic framework material 2, namely [Zn(cpt)2]. n The yield was 46.3%.
[0042] Example 3
[0043] S1. A mixed solution was prepared by mixing distilled water and acetonitrile at a volume ratio of 2:1. 0.05 mmol of ligand Hcpt and 0.05 mmol of metal salt Zn(NO3)2 were dissolved in 9 mL of the mixed solution. After stirring at room temperature for 30 min to allow the reaction to proceed, an intermediate product was obtained. The intermediate product was transferred to a high-pressure reactor lined with polytetrafluoroethylene. The temperature inside the high-pressure reactor was increased to 160 °C at a rate of 5 °C / h. The solvothermal reaction was carried out for 3 days to obtain the reaction product.
[0044] S2. The reaction product obtained in S1 is cooled and crystallized at a rate of 5 °C / h. After washing with anhydrous ethanol and filtering under reduced pressure, blocky crystals are obtained. These crystals are then dried in an oven at 60 °C for 3 hours to obtain zinc(II) metal-organic framework material 3, namely [Zn(cpt)2]. n The yield was 69.1%.
[0045] Comparative Example 1
[0046] This comparative example provides a method for preparing a zinc(II) metal-organic framework material, the specific steps of which are as follows:
[0047] S1. Distilled water and acetonitrile were mixed at a volume ratio of 2:1 to obtain a mixed solution. 0.1 mmol of ligand Hcpt and 0.05 mmol of metal salt Zn(NO3)2 were dissolved in 10 mL of the mixed solution. The mixed solution was then transferred to a high-pressure reactor lined with polytetrafluoroethylene. The temperature inside the high-pressure reactor was increased to 160 °C at a heating rate of 10 °C / h. The solvothermal reaction was carried out for 3 days to obtain the reaction product.
[0048] S2. The reaction product obtained in S1 was cooled and crystallized at a rate of 5 °C / h. After washing with anhydrous ethanol and filtering under reduced pressure, the product was dried in an oven at 60 °C for 3 h to obtain zinc(II) metal-organic framework material 4 with a yield of 32.6%.
[0049] Comparative Example 2
[0050] This comparative example provides a method for preparing a zinc(II) metal-organic framework material, the specific steps of which are as follows:
[0051] S1. Distilled water and acetonitrile were mixed at a volume ratio of 2:1 to obtain a mixed solution. 0.05 mmol of ligand Hcpt and 0.1 mmol of metal salt Zn(NO3)2 were dissolved in 10 mL of the mixed solution. The mixed solution was then transferred to a high-pressure reactor lined with polytetrafluoroethylene. The temperature inside the high-pressure reactor was increased to 180 °C at a heating rate of 10 °C / h. The solvothermal reaction was carried out for 3 days to obtain the reaction product.
[0052] S2. The reaction product obtained in S1 was cooled and crystallized at a rate of 5 °C / h. After washing with anhydrous ethanol and filtering under reduced pressure, the product was dried in an oven at 60 °C for 3 h to obtain zinc(II) metal-organic framework material 5 with a yield of 45.2%.
[0053] The products prepared in the comparative examples and the examples differed mainly in morphology, in terms of yield. Example 3 was a bulk crystal, and since powder cannot be tested as a single crystal, only the bulk crystal of Example 3 could be tested to obtain the microstructure of the material, verifying the correctness of the material structure. Furthermore, Example 3 had high purity, making it the best choice for detection and photocatalytic degradation.
[0054] Example 4
[0055] The zinc(II) metal-organic framework material 3 obtained in Example 3 was further characterized as follows:
[0056] (1) Determination of the crystal structure of zinc(II) metal-organic framework materials
[0057] Single crystals of metal-organic framework materials with clean, smooth surfaces, free of concavities and cracks were selected. At a temperature of 273±2K, a BRDUKER SMART APEX-Ⅱ CCD X-ray single crystal diffractometer was used with monochromatic Mo-Kα (wavelength 0.71073 Å) rays from graphite. Diffraction data were collected using a scanning method. All data were corrected for empirical absorption, and the crystal structure was solved using a direct method. The anisotropy parameters and coordinates of all non-hydrogen atoms were corrected using the least squares method. F2 was refined using the SHELXTL-97 program, and the coordinates of hydrogen atoms were obtained by theoretical calculations.
[0058] Detailed crystal measurement data are shown in Table 1, important bond lengths and bond angles are shown in Table 2, and the crystal structure is shown in Table 3. Figure 1 .
[0059] Table 1. Key crystallographic data of zinc(II) metal-organic framework material 3
[0060] Where R1=∑(||Fo|-|Fc||) / ∑|Fo|, wR2=[∑w(Fo) 2 -| Fc 2 ) 2 / ∑w(Fo) 2 ] 1 / 2 ;
[0061] Table 2. Important bond lengths (Å) and bond angles (°) of zinc(II) metal-organic framework materials.
[0062] In Table 1, a, b, and c represent the edge lengths of the crystal along the three crystal axes, respectively; α, β, and γ represent the angles between axes a and b, a and c, and b and c, respectively; Z is the number of molecules in a unit cell; the diffraction index range of the restriction factor is (h, k, l); F(000) is the number of electrons in a unit cell; Final R indices [I>2σ(I)] is the residual factor R value for observable diffraction points; R is the unweighted consistency factor; R1 and wR2 are both weighted consistency factors; symmetry code: 1 -X,1-Y,1-Z ;
[0063] In Table 2, the first row of bond lengths, Zn(1) refers to Zn atom 1 in zinc(II) metal-organic framework material 3, O(3A) and O(3B) refer to two different O atoms in zinc(II) metal-organic framework material 3, Zn(1)-O(3A) represents the bond length between Zn atom 1 and O atom 3A, which is 1.9561±11Å, where 11 is the standard deviation; the first row of bond angles, O(3A)-Zn(1)-O(3B), represents the bond angle between O atom 3A, Zn atom 1 and O atom 3B, which is 102.14±7.
[0064] Zn coordinates with two carboxyl oxygen atoms (O3A, O3B) from two ligands and two pyridine nitrogen atoms (N3A, N3B) from two ligands, forming a tetrahedral geometry with four coordinations, such as... Figure 1 As shown.
[0065] The bond length between Zn and oxygen atoms is 1.9561 Å, and the bond length between Zn and nitrogen atoms is 2.0424 Å.
[0066] Two (cpt) - ligands with µ2-η 1 η 1 Bridge four Zn II This forms a 17.696×17.696 square grid, with adjacent cells sharing a single Zn. II Connect them into a square grid chain, such as Figure 2 As shown; the chains are further bridged by ligands to form a two-dimensional network structure, such as... Figure 3 As shown.
[0067] From a topological perspective, if the four-coordinated Zn(II) ion is considered as a four-connected node, then the structure of the metal-organic framework material 12 can be simplified to a four-connected sql topological network, whose Schläfli symbol is (44), as shown in the figure. Figure 4As shown, the two-dimensional network structure further forms a three-dimensional supramolecular structure through π-π stacking, such as... Figure 5 As shown.
[0068] (2) Characterization of phase purity and solid-state fluorescence test of zinc(II) metal-organic framework materials
[0069] The theoretical PXRD spectrum simulated using Mercury software on single-crystal data is in perfect agreement with the experimental results from Bruker / D8Advance. Figure 6 This directly confirmed the phase purity of material 3. Since this single-crystal structure was obtained for the first time, the diffraction peak positions were not labeled. Solid-state fluorescence spectroscopy was performed on the ligand and zinc(II) metal-organic framework material 3 at room temperature. Figure 7 As shown, under 305 nm ultraviolet light excitation, the ligand exhibits the strongest emission peak at 471 nm. The fluorescence emission spectrum of zinc(II) metal-organic framework material 3 was measured under 305 nm ultraviolet light excitation. The results show that the emission peak of zinc(II) metal-organic framework material 3 is around 404 nm. The PXRD detection results are only used to judge the crystal purity by the difference between the actual and theoretical simulation.
[0070] Example 5
[0071] Weigh 2 mg of the zinc(II) metal-organic framework material 3 prepared in Example 3 by grinding, and add materials containing different amounts of M(NO3). n (M=Li + Pb 2+ , Mn 2+ Co 2+ , K + Na + Cu 2+ Cd 2+ Zn 2+ The metal salt was sonicated in DMF (N,N-dimethylformamide) solution for 30 min and then allowed to stand for one hour. The clear supernatant was then used for luminescence studies at room temperature.
[0072] The emission intensity of the complex under different ions was measured at an excitation wavelength of 345 nm. It can be seen that when Cu... 2+ In its presence, the luminescence intensity of zinc(II) metal-organic framework material 3 decreased significantly. This phenomenon indicates that the zinc(II) metal-organic framework material 3 has a significant effect on Cu. 2+ There is a clear fluorescence quenching phenomenon, such as Figure 8 As shown, Cu can be effectively detected through fluorescence quenching. 2 + . Figure 9 Zinc(II) metal-organic framework materials with different concentrations of Cu 2+The fluorescence emission spectrum of Cu ions shows that when Cu 2+ As the concentration of zinc(II) metal-organic framework material 3 increases, the fluorescence intensity decreases.
[0073] The ion quenching efficiency was further analyzed based on the Stern-Volmer equation: I0 / I = 1 + Ksv[M], where I0 and I represent the fluorescence intensity without ion solution and the emission intensity of the complex after ion solution is added, respectively, and [M] represents Cu. 2+ The concentration.
[0074] Calculations yielded 3 pairs of Cu in zinc(II) metal-organic framework materials. 2+ The Ksv value is 9.3 × 10 4 M -1 The limit of detection (LOD) was calculated based on 3σ / k (σ is the standard deviation of 10 blank tests, and k is the slope of the linear relationship). The result was Cu. 2+ The detection limit is 2.9 μM, such as Figure 10 As shown.
[0075] Example 6
[0076] Weigh the zinc(II) metal-organic framework material 3 prepared in Example 3 and add it to different small molecule organic reagents: CH3CN (acetonitrile), NB (n-butanol), CH3CH2OH (ethanol), CH3OH (methanol), DMA (N,N-dimethylacetamide), DMF (N,N-dimethylformamide), DMSO (dimethyl sulfoxide), and CH2Cl2 (dichloromethane). The results are as follows. Figure 11 As shown.
[0077] Figure 11 The images show the fluorescence emission spectra of zinc(II) metal-organic framework materials in different small molecule organic solvents. It can be seen that zinc(II) metal-organic framework material 3 exhibits obvious fluorescence quenching in the presence of NB.
[0078] Example 7
[0079] 15 mg of the zinc(II) metal-organic framework material 3 prepared in Example 3 was ground and added to a 50 mL reactor. 50 mL of 20 mg / L Rhodamine B (Rh B) was then added. After sonication for 30 min, the mixture was placed in a dark reaction chamber for 30 min, followed by a 120 min reaction under light. Samples were taken every 10 min to measure the UV-Vis absorption spectrum of the solution. Figure 12 As shown. From Figure 12It can be seen that when zinc(II) metal-organic framework materials are used as catalysts, they have a good degradation effect on rhodamine B. After 120 min of irradiation, almost 86% of rhodamine B is degraded.
[0080] To further investigate the mechanism of photocatalysis, electron paramagnetic resonance (EPR) technology was used, with DMPO as a scavenger of hydroxyl and superoxide radicals, to study the generation of free radicals in zinc(II) metal-organic framework materials under ultraviolet light irradiation. The results are as follows: Figure 13 and 14 As shown, no free radicals were detected under dark conditions; however, after 15 minutes of exposure to visible light, hydroxyl radicals (…) were detected. . OH) and superoxide radicals ( . O2 - The species were clearly identified, which facilitated the degradation of the dye by the complex.
[0081] The above description is merely a preferred embodiment of the present invention and is not intended to limit the invention in any way. Any simple modifications, alterations, and equivalent changes made to the above embodiments based on the inventive essence shall still fall within the protection scope of the present invention.
Claims
1. A zinc(II) metal-organic framework material, characterized in that, The chemical formula for the zinc(II) metal-organic framework material is [Zn(cpt)2]. n The single-crystal molecular formula of the zinc(II) metal-organic framework material is C0. 56 H 36 ZnN6O6.
2. The zinc(II) metal-organic framework material according to claim 1, characterized in that, The chemical formula for the zinc(II) metal-organic framework material contains the ligand (cpt). - The Hcpt is a deprotonated Hcpt, wherein the Hcpt is 4′-(4-(4-carboxyphenoxy)phenyl)-4,2′:6′,4″-terpyridine; The structural formula of Hcpt is: 。 3. The zinc(II) metal-organic framework material according to claim 1, characterized in that, The zinc(II) metal-organic framework material is monoclinic with space group P2 / c and cell parameters including a=12.24424(19) Å, b=6.38823(7) Å, c=31.6860(4) Å, α=90°Å, β=100.5124(14)°Å and γ=90°Å.
4. A method for preparing a zinc(II) metal-organic framework material as described in any one of claims 1-3, characterized in that, Includes the following steps: S1. Take distilled water and acetonitrile to obtain a mixed solution. Dissolve Hcpt and divalent zinc metal salt in the mixed solution. Stir at room temperature to react fully to obtain an intermediate product. Transfer the intermediate product to a reaction vessel and react at a constant temperature to obtain the reaction product. S2. After the reaction product is cooled to room temperature, it is cooled and crystallized. After washing, vacuum filtration and drying, zinc(II) metal-organic framework material is obtained.
5. The preparation method according to claim 4, characterized in that, The divalent zinc metal salt in S1 is Zn(NO3)2, the stirring reaction time is 30 min, the lining of the reaction vessel is polytetrafluoroethylene, the heating rate of the reaction vessel is 5 ℃ / h, the constant temperature reaction temperature is 160 ℃, and the constant temperature reaction time is 3 d.
6. The method for preparing the zinc(II) metal-organic framework material according to claim 4, characterized in that, In S1, the volume ratio of distilled water to acetonitrile in the mixed solution is 2:1, and the volume ratio of Hcpt, divalent zinc metal salt, and the mixed solution is 0.05–0.1 mmol: 0.05–0.1 mmol: 9 mL.
7. The method for preparing the zinc(II) metal-organic framework material according to claim 4, characterized in that, The cooling rate in S2 is 5 °C / h, the detergent used for washing is anhydrous ethanol, the drying temperature is 60 °C, and the drying time is 3 h.
8. An application of the zinc(II) metal-organic framework material as described in any one of claims 1-3, characterized in that, The zinc(II) metal-organic framework material is used for the fluorescence detection of Cu. 2+ It contains NB and can photocatalytically degrade Rhodamine B.