Difunctional fluorescent probe adsorption material as well as preparation method and application thereof

Abstract

The invention belongs to the technical field of wastewater treatment, and particularly discloses a difunctional fluorescent probe adsorption material as well as a preparation method and application thereof. The preparation method comprises the following steps: dissolving organic zircon salt in an organic polar solvent to obtain zircon salt mother liquor; adding porphyrin organic ligands and phthalic acid organic ligands into the zirconium salt mother liquor, and uniformly stirring to obtain mixed liquor; adding the mixed solution into a reaction kettle, and carrying out high-pressure solvothermal reaction, so that zirconium ions and organic ligands in the zirconium salt are subjected to homogeneous nucleation and heterogeneous nucleation; and separating, cleaning and drying to obtain the product. The difunctional fluorescent probe adsorbing material prepared by the invention has the functions of fluorescence detection and adsorption treatment on fluorine ions, and high-sensitivity quantitative analysis detection and visual treatment of the fluorine ions can be realized due to the excellent fluorescence detection effect of the difunctional fluorescent probe adsorbing material, that is, whether the concentration of the fluorine ions in effluent reaches the standard or not can be judged according to the change of the color of the effluent under ultraviolet light; and judging whether the adsorption material of the bifunctional fluorescent probe reaches adsorption saturation or not.

Description

Technical Field

[0001] The invention belongs to the technical field of wastewater treatment, and in particular relates to a dual-function fluorescent probe adsorption material capable of both fluoride ion detection and treatment, and a preparation method and application thereof. Background Art

[0002] With the development of modern industry, a large amount of fluorine-containing industrial wastewater will be generated in the production process of fluorine-related industries. However, many companies currently do not have complete water treatment facilities to treat fluorine-containing industrial wastewater, and can only discharge it into natural water bodies, resulting in a sharp increase in the content of fluoride ions in natural water bodies, seriously polluting the environment on which humans depend for survival. If people ingest high doses of fluoride for a long time, it can lead to problems such as fluorosis and bone deformation, and even cause fluoride poisoning, posing a great threat to human health. In addition, due to the different characteristics of various fluorine-related industries, fluorine-containing industrial wastewater usually has the characteristics of complex fluoride ion forms, large concentration differences, wide distribution range, and high difficulty in removal. In addition, since industrial production wastewater usually contains other pollutants such as inorganic salts or organic matter in addition to fluorine, the difficulty of its treatment is further increased, which seriously restricts the further development of the fluorine-related industry.

[0003] In recent years, the use of adsorbent materials for the adsorption and purification of drinking water has attracted more and more attention due to its low cost and simple operation. There are many adsorbent materials currently used in water treatment, including clay, zeolite, diatomaceous earth, molecular sieves, activated carbon, resins, and some nanocomposite adsorbent materials. In addition, when adsorbent materials are used for the adsorption and purification of fluoride-containing wastewater in a flowing state, they have the advantages of high purification efficiency, simplified operation, and low cost. However, the following problems still exist: First, after the conventional adsorbent material is adsorbed, it is difficult to monitor the residual fluoride ion concentration in real time in situ, and it is impossible to achieve visual processing; second, after the conventional adsorbent material is adsorbed, it is difficult to visually judge the adsorption saturation of the material, which limits the rapid and deep purification performance of fluoride ions.

[0004] Therefore, in the actual application process, we not only need to remove and separate fluoride ions in water bodies, but also need to monitor the fluoride ion concentration in the treated water bodies and whether the material is adsorbed saturated in real time to achieve visual processing. However, in the current field of fluoride ion detection and treatment, due to the obvious differences in the scientific and technological nature of the two, a single material cannot have both detection and treatment functions. By constructing functional core-shell structure materials, combining the two functions of detection and treatment into one material, and preparing a fluorescent probe adsorbent, fluoride ion detection and treatment can be accurately and effectively realized, which has important scientific significance and application value for ensuring the accurate acquisition and efficient removal of fluoride pollution information. Summary of the invention

[0005] In view of the shortcomings and deficiencies of existing fluorine removal materials that cannot simultaneously have both detection and treatment functions, the purpose of the present invention is to provide a dual-function fluorescent probe adsorption material that can detect and treat fluorine ions and a preparation method thereof.

[0006] To achieve the above object, the technical solution adopted by the present invention is: The first invention object of the present invention is to provide a method for preparing a dual-functional fluorescent probe adsorption material, which is characterized by comprising the following steps: S1, dissolving an organic zirconium salt in an organic polar solvent to obtain a zirconium salt mother solution; S2, adding porphyrin organic ligand and phthalic acid organic ligand to the zirconium salt mother liquor, stirring evenly to obtain a mixed solution; S3, adding the mixed solution into a reactor to carry out a high-pressure solvothermal reaction, so that the zirconium ions and organic ligands in the zirconium salt undergo homogeneous nucleation and heterogeneous nucleation; S4. The reactants are separated, cleaned and dried to obtain a bifunctional fluorescent probe adsorption material.

[0007] In a further embodiment, in step S1, the organic zirconium salt is at least one of zirconium acetate, zirconium propionate, zirconium citrate, zirconium tetramethacrylate, and butyl zirconate.

[0008] In a further embodiment, in step S1, the organic polar solvent is at least one of ethanol, acetone, chloroform, ether, acetic acid, acetonitrile, isopropanol, and N,N-dimethylformamide.

[0009] In a further embodiment, in step S2, the porphyrin organic ligand is at least one of tetraphenylporphyrin, tetracarboxylporphyrin, tetraaminoporphyrin, tetrapyridylporphyrin, and tetramethoxyphenylporphyrin; The phthalic acid organic ligand is at least one of terephthalic acid, isophthalic acid and phthalic acid.

[0010] In a further embodiment, in step S2, the molar ratio of the porphyrin organic ligand, the phthalic acid organic ligand and the organic zirconium salt in the mixed solution is 1:1:1-3.

[0011] In a further embodiment, in step S3, the pressure of the high pressure solvent thermal reaction is 5-8 MPa, the temperature is 120-160° C., and the time is 12-24 h.

[0012] In a further embodiment, in step S2, the stirring speed is 300-500 rpm and the time is 10-30 min; In step S4, the separation is performed by vacuum filtration; the washing is performed by continuous washing with ethanol and ultrapure water for at least 3 times; and the drying temperature is 60-80°C.

[0013] The second inventive object of the present invention is to provide a dual-functional fluorescent probe adsorption material, which is a core-shell structure Zr-MOFs material prepared by the above-mentioned preparation method.

[0014] The third invention objective of the present invention is to provide an application of the above-mentioned dual-function fluorescent probe adsorption material, which is used for the adsorption treatment of fluoride ions in fluoride-containing wastewater.

[0015] According to a further solution, in fluoride-containing wastewater with a fluoride ion concentration of 200 mg / L, the maximum adsorption capacity of the bifunctional fluorescent probe adsorption material for fluoride ions is 215.27 mg / g.

[0016] The fourth inventive object of the present invention is to provide an application of the above-mentioned dual-function fluorescent probe adsorption material, which is used for the fluorescent detection of fluoride ions in fluoride-containing wastewater.

[0017] A fifth object of the present invention is to provide an application of the above-mentioned dual-functional fluorescent probe adsorption material, which is used for visual removal of fluoride ions in fluoride-containing wastewater.

[0018] In a further embodiment, the steps for visually removing fluoride ions from fluoride-containing wastewater include: Filling the dual-function fluorescent probe adsorption material into an adsorption column; allowing the fluorine-containing wastewater to flow through the adsorption column; Under ultraviolet light, observe the colors of the inlet and outlet water of the adsorption column. When the outlet water color turns red, it indicates that the adsorption capacity of the bifunctional fluorescent probe adsorption material for fluoride ions has reached saturation, and the outlet fluoride ion concentration is less than 1 mg / L.

[0019] In a further embodiment, the fluoride ion concentration in the fluoride-containing wastewater is greater than 3 mg / L; The fluorine-containing wastewater is introduced into the adsorption column by a peristaltic pump and stays in the adsorption column for 10-30 minutes.

[0020] In a further solution, the adsorption column is a tubular structure of a transparent material, and the dual-function fluorescent probe adsorption material is filled in the middle of the adsorption column to form an adsorption material layer. Cavities are left between the two ends of the adsorption material layer and the water inlet and outlet of the adsorption column to observe the fluorescent color changes of the inlet and outlet water.

[0021] Compared with the prior art, the present invention has the following beneficial effects: The present invention mainly utilizes the difference in nucleation rates between different ligands and Zr metal centers during the preparation of zirconium-based metal organic framework compounds (Zr-MOFs), and obtains different functionalized core-shell structures of Zr-MOFs, i.e., bifunctional fluorescent probe adsorption materials, by regulating homogeneous nucleation (rapid formation of the core part) and heterogeneous nucleation (formation of the shell part on the core surface). Thus, the dual functions of fluorescence detection and adsorption treatment of fluoride ions are achieved, and rapid adsorption, highly sensitive quantitative analysis and detection, and visualization of fluoride ions can be achieved, solving the bottleneck problem that it is difficult to monitor the residual fluoride ion concentration and the adsorption saturation of the material in real time in situ after the adsorption of conventional materials is completed, and the visualization treatment cannot be achieved.

[0022] The present invention selects an organic zirconium source with rich hydroxyl groups, carboxyl groups and carbon chains on its surface, and reacts it with two different ligands for nucleation reaction; utilizes the difference in nucleation rates of different ligands to achieve a one-step reaction of homogeneous nucleation (rapid formation of the core body part, fluorescence detection unit) and heterogeneous nucleation (formation of the shell part on the core body surface, adsorption enrichment unit), and obtains a dual-functional fluorescent probe adsorption material of core-shell structured Zr-MOFs.

[0023] The bifunctional fluorescent probe adsorption material prepared by the present invention has both the functions of fluorescence detection (core part) and adsorption treatment (shell part) of fluoride ions. Its excellent fluorescence detection effect can realize highly sensitive quantitative analysis and detection and visualization of fluoride ions, that is, under ultraviolet light, it can be judged whether the fluoride ion concentration in the effluent water meets the standard (less than 1 mg / L) and whether the bifunctional fluorescent probe adsorption material has reached adsorption saturation according to the change of the effluent color.

[0024] The bifunctional fluorescent probe adsorption material synthesized by the present invention is a core-shell structure Zr-MOFs, and the active groups such as hydroxyl and carboxyl groups on the surface shell part are greatly increased, which overcomes the defect of slow adsorption rate of fluoride ions by conventional adsorption materials. Thus, the rate and efficiency of adsorption of fluoride ions are greatly improved, and rapid adsorption and removal of fluoride ions can be achieved. In addition, the excellent adsorption performance of the shell part can also achieve enrichment, further improving the fluorescence detection effect of the core part. BRIEF DESCRIPTION OF THE DRAWINGS

[0025] Figure 1 This is a SEM image of the dual-functional fluorescent probe adsorption material prepared in Example 1; Figure 2 The adsorption performance curve of the dual-function fluorescent probe adsorption material prepared in Example 1 to fluoride ions; Figure 3 The fluorescence detection performance curve of the dual-function fluorescent probe adsorption material prepared in Example 1 for fluoride ions; Figure 4 This is a schematic diagram of the structure of the visualization removal device in Experimental Example 4. DETAILED DESCRIPTION

[0026] The present invention is further described below in conjunction with the embodiments. Obviously, the described embodiments are only a part of the embodiments of the present invention, rather than all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0027] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by technicians in the technical field to which the present invention belongs. The terms used in the specification of the present invention are only for the purpose of describing specific embodiments and are not intended to limit the present invention.

[0028] Embodiment 1: A method for preparing a dual-functional fluorescent probe adsorption material comprises the following steps: S1, dissolving 32.74 g of zirconium acetate in 500 mL of ethanol solution to obtain a zirconium acetate mother solution; S2. Add 61.47 g of tetraphenylporphyrin and 16.61 g of terephthalic acid organic ligand to the zirconium acetate mother liquor; stir at 300 rpm for 20 min to obtain a mixed solution (the molar ratio of the porphyrin organic ligand, the phthalic acid organic ligand and the organic zirconium salt in the mixed solution is 1:1:1); S3, adding the mixed solution into a high-pressure reactor for high-pressure solvent thermal reaction, wherein the pressure is 5 MPa, the temperature is 120° C., and the time is 12 h; S4. After cooling the reactants to room temperature, vacuum filtration is performed to separate the solid product, which is then washed three times with ethanol and ultrapure water, and then placed in an oven at 60°C for drying to obtain a dual-functional fluorescent probe adsorption material.

[0029] Test Example 1: The morphology of the dual-functional fluorescent probe adsorption material prepared in Example 1 was characterized by scanning electron microscopy (SEM image). Figure 1 As shown, it can be seen that the prepared bifunctional fluorescent probe adsorption material is a polyhedral morphology of core-shell structure Zr-MOFs, which is consistent with the structural characteristics of MOFs.

[0030] Test Example 2: The bifunctional fluorescent probe adsorbent material prepared in Example 1 was subjected to an adsorption capacity measurement experiment in fluoride-containing wastewater at different temperatures and different fluoride ion concentrations. Specifically, 12 portions of 1L of fluoride-containing wastewater were first prepared, wherein the initial fluoride ion concentration (C0) was 1, 2, 3, 5, 10, 20, 30, 50, 80, 100, 150, and 200 mg / L, respectively; then, 0.5g (m) of the bifunctional fluorescent probe adsorbent material prepared in Example 1 was added to each of the 12 portions of fluoride-containing wastewater; then, the process was repeated three times, and the mixture was stirred at 25°C, 35°C, and 45°C for 30 minutes, and then the supernatant was taken after standing, and the fluoride ion concentration C1 of each portion was detected by the ion selective electrode method. The detection results are shown as follows: Figure 2 As shown (the equilibrium concentration on the horizontal axis in the figure is C1, which is the fluoride ion concentration of the above-mentioned fluoride-containing wastewater after being adsorbed by the bifunctional fluorescent probe adsorption material).

[0031] from Figure 2 It can be seen that with the increase of fluoride ion concentration, the adsorption capacity of the dual-functional fluorescent probe adsorbent material for fluoride ions gradually increases; and with the increase of temperature, the adsorption capacity of the dual-functional fluorescent probe adsorbent material for fluoride ions also increases slightly. When the fluoride ion concentration in the fluoride-containing wastewater is 200 mg / L and the temperature is 45°C, the equilibrium concentration after adsorption by the dual-functional fluorescent probe adsorbent material is 92.36 mg / L, and the maximum adsorption capacity of the dual-functional fluorescent probe adsorbent material for fluoride ions ((C0-C1) / m) reaches 215.28 mg / g.

[0032] Test Example 3: 10 mg of the bifunctional fluorescent probe adsorbent prepared in Example 1 was dispersed in 50 mL of deionized water and ultrasonicated for 30 min to form a uniform suspension (0.2 mg / mL), which was stored in a refrigerator at 277 K for subsequent use.

[0033] In the fluorescence detection step, first take 2.0 mL of the prepared dual-function fluorescent probe adsorption material suspension and place it in a quartz test tube; then take 0-220 μL of a 30 mg / L fluoride solution and gradually add it to the quartz test tube for mixing, so that the fluoride ion concentration in the mixed solution is 0-3 mg / L. Use the American Cary Eclipse fluorescence spectrophotometer at room temperature to immediately record the fluorescence spectrum, such as Figure 3 shown.

[0034] from Figure 3 It can be seen from the figure that in the process of fluorescence detection of fluoride ions, fluoride ions have a good fluorescence quenching performance on the dual-functional fluorescent probe adsorption material. - As the concentration gradually increases (from 0 to 3 mg / L), the fluorescence intensity of the fluorescent probe adsorbent material decays rapidly. -When the concentration was 3 mg / L, the fluorescence intensity quenching efficiency of the fluorescent probe adsorption material at the 654nm emission peak reached 55%; at the same time, its fluorescence color changed from red in the inlet water to blue in the outlet water. - The concentration showed a good linear relationship (R 2 = 0.995), which can be used for highly sensitive quantitative analysis and detection of fluoride ions.

[0035] Test example 4: The dual-function fluorescent probe adsorption material prepared in Example 1 was used in the visual removal test of fluorine-containing wastewater. Figure 4 The visual removal device shown is carried out, and the steps include: S1. Fill 200g of dual-function fluorescent probe adsorption material into the adsorption column 5 made of transparent glass to form an adsorption material layer 7. The two ends of the adsorption material layer 7 are filled with sponges 6 respectively. There are cavities between the sponges 6 at both ends of the adsorption material layer 7 and the water inlet and outlet of the adsorption column to observe the fluorescent color changes of the inlet and outlet water. The adsorption column 5 is built into the protective cover 2. An ultraviolet lamp 3 is installed inside the protective cover 2 located above the adsorption column 5. An observation window 4 is opened on the protective cover 2. The water inlet of the adsorption column 5 is connected to the fluorine-containing wastewater tank through a peristaltic pump 1, and the water outlet is connected to the treated water tank; S2, using a peristaltic pump 1 to introduce fluoride-containing wastewater with a fluoride ion concentration of 5 mg / L into the adsorption column 5, and leaving it in the adsorption column 5 for 10 minutes; S3. Under the light of the ultraviolet lamp 3, when the water color of the adsorption column 5 is observed to be blue and the water color of the outlet is red through the observation window 4, it indicates that the fluoride ion concentration in the outlet water is lower than 1 mg / L at this time, and the dual-function fluorescent probe adsorption material has reached adsorption saturation.

[0036] Example 2 A method for preparing a dual-functional fluorescent probe adsorption material comprises the following steps: S1, dissolving 38.35 g of zirconium propionate in 500 mL of acetone solution to obtain a zirconium propionate mother solution; S2. Add 84.37 g of tetracarboxyl porphyrin and 16.61 g of terephthalic acid organic ligand to the zirconium propionate mother liquor; stir at 500 rpm for 20 min to obtain a mixed solution (the molar ratio of porphyrin organic ligand, phthalic acid organic ligand and organic zirconium salt in the mixed solution is 1:1:1); S3, adding the mixed solution into a high-pressure reactor for high-pressure solvent thermal reaction, wherein the pressure is 8 MPa, the temperature is 160° C., and the time is 12 h; S4. After cooling the reactants to room temperature, vacuum filtration is performed to separate the solid product, which is then washed three times with ethanol and ultrapure water, and then placed in an oven at 60°C for drying to obtain a dual-functional fluorescent probe adsorption material.

[0037] The dual-function fluorescent probe adsorption material prepared in Example 2 was tested for adsorption and removal of fluoride ions from fluoride-containing wastewater with different fluoride ion concentrations at 45°C according to the detection method of Test Example 2. After testing, when the initial fluoride ion concentration was 200 mg / L, its maximum adsorption capacity reached 201.28 mg / g.

[0038] According to the detection method of Experimental Example 3, the fluorescence detection was performed on it. The detection showed that the dual-function fluorescent probe adsorption material prepared in this embodiment had excellent fluorescence detection performance. - As the concentration gradually increased (0-3 mg / L), the fluorescence intensity decayed rapidly, indicating that the fluorescence intensity was related to F - The concentrations show a good linear relationship and can be used for highly sensitive quantitative analysis and detection of fluoride ions.

[0039] Test Example 5: The dual-function fluorescent probe adsorption material prepared in Example 2 was used in a visual removal test of fluorine-containing wastewater, using the same visual removal device as in Experimental Example 4, and the steps were as follows: S1. Fill 200g of dual-function fluorescent probe adsorption material into a transparent glass adsorption column; S2. Use a peristaltic pump to introduce fluoride-containing wastewater with a fluoride ion concentration of 8 mg / L into the adsorption column and keep it in the adsorption column for 20 minutes; S3. Under the light of ultraviolet lamp, it is observed that the color of the water entering the adsorption column is blue, while the color of the water leaving the column is red, indicating that the fluoride ion concentration in the water leaving the column is lower than 1 mg / L, and the dual-function fluorescent probe adsorption material has reached adsorption saturation.

[0040] Embodiment 3: A method for preparing a dual-functional fluorescent probe adsorption material comprises the following steps: S1, dissolving 103.01 g of zirconium citrate in 500 mL of N,N-dimethylformamide solution to obtain a zirconium citrate mother solution; S2. Add 67.47 g of tetraaminoporphyrin and 16.61 g of terephthalic acid organic ligand to the zirconium citrate mother liquor; stir at 500 rpm for 30 min to obtain a mixed solution (the molar ratio of porphyrin organic ligand, phthalic acid organic ligand and organic zirconium salt in the mixed solution is 1:1:1); S3, adding the mixed solution into a high pressure reactor for solvothermal reaction at a pressure of 5 MPa, a temperature of 140°C and a time of 12 h; S4. After cooling the reactants to room temperature, vacuum filtration is performed to separate the solid product, which is then washed three times with ethanol and ultrapure water, and then dried in an oven at 60°C to obtain a dual-functional fluorescent probe adsorption material.

[0041] The dual-function fluorescent probe adsorption material prepared in Example 3 was tested for adsorption and removal of fluoride ions from fluoride-containing wastewater with different fluoride ion concentrations at 45°C according to the detection method of Test Example 2. After testing, when the initial fluoride ion concentration was 200 mg / L, the maximum adsorption amount reached 192.83 mg / g.

[0042] The fluorescence detection was performed according to the detection method of Experimental Example 3. The results showed that the dual-function fluorescent probe adsorption material prepared in this embodiment had excellent fluorescence detection performance. - As the concentration gradually increased (0-3 mg / L), the fluorescence intensity of the material rapidly decayed, indicating that the fluorescence intensity was related to F - The concentrations show a good linear relationship and can be used for highly sensitive quantitative analysis and detection of fluoride ions.

[0043] Test Example 6: The dual-function fluorescent probe adsorption material prepared in Example 3 was used in the visual removal test of fluorine-containing wastewater, and the visual removal device of Experimental Example 4 was used, specifically: S1. Fill 200g of dual-function fluorescent probe adsorption material into a transparent glass adsorption column; S2. Use a peristaltic pump to introduce fluoride-containing wastewater with a fluoride ion concentration of 10 mg / L into the adsorption column and keep it in the adsorption column for 30 minutes; S3. Under ultraviolet light, it is observed that the color of the water entering the adsorption column is blue, while the color of the water leaving the column is red, indicating that the fluoride ion concentration in the water leaving the column is lower than 1 mg / L, and the dual-function fluorescent probe adsorption material has reached adsorption saturation.

[0044] Embodiment 4: A method for preparing a dual-functional fluorescent probe adsorption material comprises the following steps: S1. Dissolve 97.22 g of zirconium acetate in 500 mL of ether solution to obtain a zirconium acetate mother solution; S2. Add 61.87 g of tetrapyridine porphyrin and 16.61 g of phthalic acid organic ligand to the zirconium acetate mother liquor; stir at 300 rpm for 20 min to obtain a mixed solution (the molar ratio of porphyrin organic ligand, phthalic acid organic ligand and organic zirconium salt in the mixed solution is 1:1:3); S3, adding the mixed solution into a high pressure reactor for solvothermal reaction at a pressure of 6 MPa, a temperature of 120°C and a time of 16 h; S4. After cooling the reactants to room temperature, vacuum filter and separate the solid product, wash it three times with ethanol and ultrapure water, and then dry it in an oven at 60°C to obtain a dual-functional fluorescent probe adsorption material for fluoride ion detection and treatment.

[0045] The dual-function fluorescent probe adsorption material prepared in Example 4 was tested for adsorption and removal of fluoride ions from fluoride-containing wastewater with different fluoride ion concentrations at 45°C according to the detection method of Test Example 2. After testing, when the initial fluoride ion concentration was 200 mg / L, the maximum adsorption amount could reach 208.48 mg / g.

[0046] The fluorescence detection was performed according to the detection method of Experimental Example 3. The results showed that the dual-function fluorescent probe adsorption material prepared in this embodiment had excellent fluorescence detection performance. - As the concentration gradually increased (0-3 mg / L), the fluorescence intensity of the material rapidly decayed, indicating that the fluorescence intensity was related to F - The concentrations show a good linear relationship and can be used for highly sensitive quantitative analysis and detection of fluoride ions.

[0047] Example 5 A method for preparing a dual-functional fluorescent probe adsorption material comprises the following steps: S1, dissolving 43.16 g of zirconium tetramethacrylate in 500 mL of isopropanol solution to obtain zirconium tetramethacrylate mother solution; S2. Add 67.47 g of tetraaminoporphyrin and 16.61 g of isophthalic acid organic ligand to the tetramethylacrylate zirconium mother liquor; stir at 300 rpm for 30 min to obtain a mixed solution (the molar ratio of the porphyrin organic ligand, the phthalic acid organic ligand and the organic zirconium salt in the mixed solution is 1:1:1); S3, adding the mixed solution into a high pressure reactor for solvothermal reaction at a pressure of 8 MPa, a temperature of 120°C and a time of 24 h; S4. After cooling the reactants to room temperature, vacuum filtration is performed to separate the solid product, which is then washed three times with ethanol and ultrapure water, and then dried in an oven at 60°C to obtain a dual-functional fluorescent probe adsorption material.

[0048] The bifunctional fluorescent probe adsorption material prepared in Example 5 was tested according to the detection method of Experimental Example 2 for adsorption and removal of fluoride ions from fluoride-containing wastewater with different fluoride ion concentrations at 45°C. When the initial fluoride ion concentration was 200 mg / L, the maximum adsorption amount reached 206.39 mg / g.

[0049] The fluorescence detection was performed according to the detection method of Experimental Example 3. The results showed that the dual-function fluorescent probe adsorption material prepared in this embodiment had excellent fluorescence detection performance. - As the concentration gradually increased (0-3 mg / L), the fluorescence intensity of the material rapidly decayed, indicating that the fluorescence intensity was related to F - The concentrations show a good linear relationship and can be used for highly sensitive quantitative analysis and detection of fluoride ions.

[0050] Embodiment 6: A method for preparing a dual-functional fluorescent probe adsorption material comprises the following steps: S1. Dissolve 65.48 g zirconium acetate in 500 mL DMF (N,N-dimethylformamide) solution to obtain zirconium acetate mother solution; S2. Add 67.47 g of tetraaminoporphyrin and 16.61 g of isophthalic acid organic ligand to the zirconium acetate mother liquor; stir at 500 rpm for 10 min to obtain a mixed solution (the molar ratio of the porphyrin organic ligand, the phthalic acid organic ligand and the organic zirconium salt in the mixed solution is 1:1:2); S3, adding the mixed solution into a high pressure reactor for solvothermal reaction at a pressure of 5 MPa, a temperature of 120°C and a time of 24 h; S4. After cooling the reactants to room temperature, vacuum filtration is performed to separate the solid product, which is then washed four times with ethanol and ultrapure water, and then dried in an oven at 80°C to obtain a dual-functional fluorescent probe adsorption material.

[0051] The dual-function fluorescent probe adsorption material prepared in Example 6 was tested for adsorption and removal of fluoride ions from fluoride-containing wastewater with different fluoride ion concentrations at 45°C according to the detection method of Test Example 2. After testing, when the initial fluoride ion concentration was 200 mg / L, the maximum adsorption amount reached 201.61 mg / g.

[0052] The fluorescence detection was performed according to the detection method of Experimental Example 3. The results showed that the dual-function fluorescent probe adsorption material prepared in this embodiment had excellent fluorescence detection performance. - As the concentration gradually increased (0-3 mg / L), the fluorescence intensity of the material rapidly decayed, indicating that the fluorescence intensity was related to F - The concentrations show a good linear relationship and can be used for highly sensitive quantitative analysis and detection of fluoride ions.

[0053] Comparative Example 1: A method for preparing an adsorbent material comprises the following steps: S1, dissolving 65.48 g zirconium acetate in 500 mL DMF solution to obtain zirconium acetate mother solution; S2. Add 16.61 g of isophthalic acid organic ligand to the zirconium acetate mother liquor; stir at 500 rpm for 10 min to obtain a mixed solution; S3, adding the reactants into a high pressure reactor for solvothermal reaction at a pressure of 5 MPa, a temperature of 120°C, and a time of 24 h; S4. After cooling the reactants to room temperature, vacuum filtration is performed to separate the solid product, which is then washed three times with ethanol and ultrapure water, and then placed in an oven at 80°C for drying to obtain the adsorption material.

[0054] The adsorption material prepared in Comparative Example 1 was tested for adsorption and removal of fluoride ions from fluoride-containing wastewater with different fluoride ion concentrations at 45°C according to the detection method of Test Example 2. According to the test, when the initial fluoride ion concentration was 200 mg / L, the maximum adsorption amount reached 174.28 mg / g.

[0055] According to the detection method of Experimental Example 3, it was subjected to fluorescence detection. After detection, it had no fluorescence detection performance. - The fluorescence intensity of the material did not change with the gradual increase in concentration (0-3 mg / L).

[0056] Comparative Example 2: A method for preparing an adsorbent material comprises the following steps: S1, dissolving 65.48 g zirconium acetate in 500 mL DMF solution to obtain zirconium acetate mother solution; S2, adding 67.47 g of tetraaminoporphyrin organic ligand to the zirconium acetate mother liquor; stirring at 300 rpm for 30 min to obtain a mixed solution; S3, adding the reactants into a high pressure reactor for solvothermal reaction at a pressure of 5 MPa, a temperature of 140°C, and a time of 24 h; S4. After cooling the reactants to room temperature, vacuum filtration is performed to separate the solid product, which is washed three times with ethanol and ultrapure water, and dried in an oven at 60°C to obtain the adsorption material.

[0057] The adsorption material prepared in Comparative Example 2 was tested for adsorption and removal of fluoride ions from fluoride-containing wastewater with different fluoride ion concentrations at 45°C according to the detection method of Test Example 2. After testing, when the initial fluoride ion concentration was 200 mg / L, the maximum adsorption amount was only 34.86 mg / g, and the adsorption performance was poor.

[0058] According to the detection method of Experimental Example 3, the fluorescence detection was carried out on it. After the detection, it had excellent fluorescence detection performance. - As the concentration gradually increased (0-3 mg / L), the fluorescence intensity of the material rapidly decayed, indicating that the fluorescence intensity was related to F - The concentrations show a good linear relationship and can be used for highly sensitive quantitative analysis and detection of fluoride ions.

[0059] The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention. Any modification, equivalent substitution or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.

Claims

1. A method for preparing a dual-functional fluorescent probe adsorption material, characterized in that: The following steps are involved: S1, dissolving an organic zirconium salt in an organic polar solvent to obtain a zirconium salt mother solution; S2, adding porphyrin organic ligand and phthalic acid organic ligand to the zirconium salt mother liquor, stirring evenly to obtain a mixed solution; S3, adding the mixed solution into a reactor to carry out a high-pressure solvothermal reaction, so that the zirconium ions and organic ligands in the zirconium salt undergo homogeneous nucleation and heterogeneous nucleation; S4. The reactants are separated, cleaned and dried to obtain a bifunctional fluorescent probe adsorption material.

2. The preparation method according to claim 1, characterized in that: In step S1, the organic zirconium salt is at least one of zirconium acetate, zirconium propionate, zirconium citrate, zirconium tetramethacrylate, and butyl zirconate.

3. The preparation method according to claim 1, characterized in that: In step S1, the organic polar solvent is at least one of ethanol, acetone, chloroform, ether, acetic acid, acetonitrile, isopropanol, and N,N-dimethylformamide.

4. The preparation method according to claim 1, characterized in that: In step S2, the porphyrin organic ligand is at least one of tetraphenylporphyrin, tetracarboxylporphyrin, tetraaminoporphyrin, tetrapyridylporphyrin, and tetramethoxyphenylporphyrin; The phthalic acid organic ligand is at least one of terephthalic acid, isophthalic acid and phthalic acid.

5. The preparation method according to claim 1, characterized in that: In step S2, the molar ratio of the porphyrin organic ligand, the phthalic acid organic ligand and the organic zirconium salt in the mixed solution is 1:1:1-3.

6. The preparation method according to claim 1, characterized in that: In step S3, the pressure of the high-pressure solvent thermal reaction is 5-8 MPa, the temperature is 120-160° C., and the time is 12-24 h.

7. The preparation method according to claim 1, characterized in that: In step S2, the stirring speed is 300-500 rpm, and the time is 10-30 min; In step S4, the separation is performed by vacuum filtration; the washing is performed by continuous washing with ethanol and ultrapure water for at least 3 times; and the drying temperature is 60-80°C.

8. A dual-function fluorescent probe adsorption material, characterized in that: A core-shell structured Zr-MOFs material prepared by the preparation method according to any one of claims 1 to 7.

9. The use of a dual-function fluorescent probe adsorption material as claimed in claim 8, characterized in that: It is used for the adsorption treatment of fluoride ions in fluoride-containing wastewater.

10. The use according to claim 9, characterized in that: In fluoride-containing wastewater with a fluoride ion concentration of 200 mg / L, the maximum adsorption capacity of the dual-functional fluorescent probe adsorption material for fluoride ions is 215.27 mg / g.

11. The use of a dual-function fluorescent probe adsorption material as claimed in claim 8, characterized in that: It is used for fluorescence detection of fluoride ions in fluoride-containing wastewater.

12. The use of a dual-function fluorescent probe adsorption material as claimed in claim 8, characterized in that: It is used for visual removal of fluoride ions in fluoride-containing wastewater.

13. The use according to claim 12, characterized in that: The steps for visual removal of fluoride ions from fluoridated wastewater include: Filling the dual-function fluorescent probe adsorption material into an adsorption column; allowing the fluorine-containing wastewater to flow through the adsorption column; Under ultraviolet light, observe the colors of the inlet and outlet water of the adsorption column. When the outlet water color turns red, it indicates that the adsorption capacity of the bifunctional fluorescent probe adsorption material for fluoride ions has reached saturation, and the outlet fluoride ion concentration is less than 1 mg / L.

14. The use according to claim 13, characterized in that: The fluoride ion concentration in the fluoride-containing wastewater is greater than 3 mg / L; The fluorine-containing wastewater is introduced into the adsorption column by a peristaltic pump and stays in the adsorption column for 10-30 minutes.

15. The use according to claim 13, characterized in that: The adsorption column is a tubular structure made of transparent material. The dual-function fluorescent probe adsorption material is filled in the middle of the adsorption column to form an adsorption material layer. Cavities are left between the two ends of the adsorption material layer and the water inlet and outlet of the adsorption column to observe the fluorescent color changes of the inlet and outlet water.

Images