Preparation method and application of fluorescent ZET-MOGs material

Abstract

The invention relates to a preparation method and application of a fluorescent ZET-MOGs material, and the method comprises the following steps: placing ZrOCl2. 8H2O in a glass container, fully dissolving ZrOCl2. 8H2O by using deionized water and ultrasonic treatment, and naming as a solution A; 2, 4, 6-tri (4-carboxyl phenyl)-1, 3, 5-triazine (TATB) is placed in deionized water, triethylamine is added and subjected to ultrasonic treatment to be fully dissolved, and a solution B is obtained; mixing the solution A and the solution B according to a volume ratio of 1: 1 to form Zr-MOGs wet gel; the obtained wet gel is washed with deionized water, and Zr-MOGs powder is obtained through freeze drying; eu (NO3) 3.6 H2O and Tb (NO3) 3.6 H2O are dissolved in ethyl alcohol, then Zr-MOGs powder is added, stirring and centrifugal separation are carried out, washing is carried out with ethyl alcohol, and finally light yellow fluorescent ZET-MOGs powder is obtained through vacuum drying. The ZET-MOGs prepared by the preparation method disclosed by the invention has a relatively large specific surface area, relatively high porosity, rich surface functional groups and stable fluorescence response characteristics, and shows efficient removal efficiency and sensitive detection capability on CTC in a water body.

Description

Technical Field

[0001] The present invention belongs to the field of preparation of nanomaterials and environmental materials, and relates to a preparation method of fluorescent ZET-MOGs, the application of fluorescent ZET-MOGs in the ratio detection of CTC in aqueous solution, and the application of adsorbing and removing CTC in aqueous solution. Among them, "ZET" is an abbreviation of the element symbols Zr, Eu, and Tb. ZET-MOGs means a ternary metal-organic gel of zirconium, europium, and terbium. Background Art

[0002] The wide application of antibiotics has brought significant environmental problems in the medical and aquaculture industries. In particular, the persistent residues of tetracycline antibiotics represented by chlortetracycline hydrochloride (CTC) in water pose a serious threat to human health and the ecosystem. At present, the development of efficient and economical sewage treatment technologies has become an urgent task. The adsorption method is simple to operate, low in cost, and easy to obtain materials, and is regarded as an ideal choice for removing antibiotics in water.

[0003] Metal-Organic gels (MOGs), as novel functional materials, form porous structures through the self-assembly of metal ions and organic ligands, have rich active sites and easily modified surface functional groups, and show great potential in the fields of environmental remediation and monitoring; notably, their unique optical properties, especially when introducing lanthanide elements (Ln³⁺) as emission centers, make it possible to perform adsorption and detection simultaneously; compared with the traditional single Ln³⁺ system, the dual Ln³⁺ system can achieve ratio-type fluorescence detection, effectively eliminate environmental interference through the built-in reference signal, and significantly improve the detection accuracy; it should be noted that it is difficult to integrate multiple functions into a single material, and most studies only focus on detecting or adsorbing antibiotics. The successful synthesis and functional regulation of dual-lanthanide MOGs still need to be explored in depth. Summary of the Invention

[0004] Aiming at the problems existing in the above background art, the present invention provides a preparation method and application of a fluorescent ZET-MOGs material. The preparation method is simple and the reaction conditions are mild. The obtained ZET-MOGs material exhibits a large specific surface area, excellent porosity structure, rich surface functional groups, and stable fluorescence characteristics; compared with traditional single-functional materials, the present invention significantly improves the resource utilization rate and simultaneously realizes the dual functions of pollutant removal and real-time monitoring.

[0005] A preparation method of a fluorescent ZET-MOGs material includes the following steps: Step 1: Weigh 0.6445 g of ZrOCl2·8H2O and place it in a glass container. Add 20 mL of deionized water and sonicate to dissolve it completely, naming it Solution A. Step 2: Weigh 0.8828 g of 2,4,6-tris(4-carboxyphenyl)-1,3,5-triazine (TATB) and place it in 20 mL of deionized water. Add 1 mL of triethylamine and sonicate to dissolve it completely, naming it Solution B. Step 3: Mix Solutions A and B in a volume ratio of 1:1, and Zr-MOGs wet gel forms rapidly. Step 4: Wash the obtained Zr-MOGs wet gel with deionized water 3 - 5 times to remove uncoordinated metal ions and ligands, and obtain Zr-MOGs powder by freeze-drying. Step 5: Weigh 2.4534 g of Eu(NO3)3·6H2O and 2.4917 g of Tb(NO3)3·6H2O and dissolve them in 55 mL of ethanol. Then add 0.8828 g of Zr-MOGs powder, stir for 24 h, centrifuge and separate, wash with ethanol, and finally transfer the material to a vacuum drying oven at 60 °C for 3 h to obtain light yellow fluorescent ZET-MOGs powder.

[0006] The application of the fluorescent ZET-MOGs material prepared by the present invention in the ratio detection of CTC in aqueous solution and the application in the adsorption and removal of CTC in aqueous solution.

[0007] When the fluorescent ZET-MOGs prepared by the present invention adsorbs and removes CTC in aqueous solution, the dosage of ZET-MOGs in aqueous solution is 1.0 g / L, and the adsorption temperature is 298 K.

[0008] The beneficial effects of the present invention are as follows: The fluorescent ZET-MOGs prepared by the present invention are synthesized by an impregnation strategy, and the preparation process is simple. This material innovatively realizes the dual functions of ratio detection and adsorption and removal of CTC in water, providing a new solution for practical water treatment applications.

[0009] From Figure 1 、 Figure 2 、 Figure 3 、 Figure 4 and Figure 5 it can be concluded that the fluorescent ZET-MOGs prepared by the present invention have the following beneficial technical effects: 1. Large specific surface area and hierarchical porous structure; 2. Abundant surface functional groups and good thermal stability; 3. Excellent fluorescence response ability; 4. The saturated adsorption capacity for CTC can reach 406.50 mg / g.

[0010] The case results show that the fluorescent ZET-MOGs material prepared by the present invention, with its large specific surface area, multi-level pore structure, rich active sites and excellent thermal stability, innovatively integrates the dual functions of ratio fluorescence detection and efficient adsorption and removal, and exhibits excellent comprehensive performance in the remediation of CTC-polluted wastewater. Description of the Drawings

[0011] Figure 1 It is the N2 adsorption-desorption curve and pore size distribution diagram of the fluorescent ZET-MOGs prepared by the present invention; Figure 2 It is the infrared spectrum diagram of the fluorescent ZET-MOGs prepared by the present invention; Figure 3 It is the thermogravimetric curve diagram of the fluorescent ZET-MOGs prepared by the present invention; Figure 4 It is the emission spectrum diagram of the fluorescent ZET-MOGs prepared by the present invention; Figure 5 It is the adsorption performance diagram of the fluorescent ZET-MOGs prepared by the present invention for CTC. Detailed Embodiments

[0012] A preparation method of a fluorescent ZET-MOGs material comprises the following steps: Step 1: Weigh 0.6445 g of ZrOCl2·8H2O and place it in a glass container, add 20 mL of deionized water and ultrasonically dissolve it sufficiently, and name it solution A; Step 2: Weigh 0.8828 g of 2,4,6-tris(4-carboxyphenyl)-1,3,5-triazine (TATB) and place it in 20 mL of deionized water, add 1 mL of triethylamine and ultrasonically dissolve it sufficiently, and name it solution B; Step 3: Mix solutions A and B in a volume ratio of 1:1, and Zr-MOGs wet gel is rapidly formed; Step 4: Wash the obtained Zr-MOGs wet gel with deionized water 3 - 5 times to remove uncoordinated metal ions and ligands, and obtain Zr-MOGs powder by freeze-drying; Step 5: Weigh 2.4534 g of Eu(NO3)3·6H2O and 2.4917 g of Tb(NO3)3·6H2O and dissolve them in 55 mL of ethanol, then add 0.8828 g of Zr-MOGs powder, stir for 24 h, centrifuge and separate, wash with ethanol, and finally transfer the material to a vacuum drying oven at 60 °C for 3 h to obtain light yellow fluorescent ZET-MOGs powder.

[0013] Application of the prepared fluorescent ZET-MOGs material in the ratio detection of CTC in aqueous solution and in the adsorption and removal of CTC in aqueous solution.

[0014] In practical applications, the removal effect of ZET-MOGs as an adsorbent on CTC in aqueous solution can be tested by the following scheme: 1.0 g / L of ZET-MOGs was added to CTC solutions with concentrations of 50 mg / L, 100 mg / L, 150 mg / L, 200 mg / L, 250 mg / L, 300 mg / L, 350 mg / L, and 400 mg / L respectively, and shaken in the dark under the condition of constant temperature at 298 K; after reaching equilibrium, the samples were taken and filtered through a 0.22 μm filter membrane, and the remaining concentration of CTC in the solution was measured by an ultraviolet spectrophotometer (365 nm), and the adsorption capacity of ZET-MOGs at different CTC concentrations could be obtained. The maximum adsorption capacity of ZET-MOGs calculated according to the Langmuir adsorption model was 155.52 mg / g.

[0015] The detection effect of ZET-MOGs as a fluorescent probe on CTC in aqueous solution can be tested by the following scheme: 1.0 g / L of the sample was added to CTC solutions with concentrations of 10 mg / L, 20 mg / L, 30 mg / L, 40 mg / L, and 50 mg / L respectively. Under ultraviolet irradiation at 365 nm, it could be observed that the fluorescence of ZET-MOGs gradually changed from red to yellow.

Claims

1. A preparation method of a fluorescent ZET-MOGs material, characterized in that: It includes the following steps: Step 1: Weigh 0.6445 g of ZrOCl2·8H2O and place it in a glass container. Add 20 mL of deionized water and ultrasonically dissolve it to make a solution named Solution A; Step 2: Weigh 0.8828 g of 2,4,6-tris(4-carboxyphenyl)-1,3,5-triazine (TATB) and place it in 20 mL of deionized water. Add 1 mL of triethylamine and ultrasonically dissolve it to make a solution named Solution B; Step 3: Mix Solutions A and B in a volume ratio of 1:1, and Zr-MOGs wet gel is rapidly formed; Step 4: Wash the obtained wet gel with deionized water 3 - 5 times to remove uncoordinated metal ions and ligands, and obtain Zr-MOGs powder by freeze-drying; Step 5: Weigh 2.4534 g of Eu(NO3)3·6H2O and 2.4917 g of Tb(NO3)3·6H2O and dissolve them in 55 mL of ethanol. Then add 0.8828 g of Zr-MOGs powder, stir for 24 h, centrifuge and separate, wash with ethanol, and finally transfer the material to a vacuum drying oven at 60 °C for 3 h to obtain light yellow ZET-MOGs powder.

2. Applications of the fluorescent ZET-MOGs material prepared by the method described in Claim 1 in the ratio detection of CTC in aqueous solution and in the adsorption and removal of CTC in aqueous solution.

3. When the fluorescent ZET-MOGs material according to claim 2 is used for adsorbing and removing CTC in an aqueous solution, it is characterized in that: The dosage of the ZET-MOGs in aqueous solution is 1.0 g / L, and the adsorption temperature is 298 K.

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