Preparation method of magnetic organic framework material and application of magnetic organic framework material to adsorption of bisphenol A
The preparation of magnetic covalent organic frame materials by ultrasonication has solved the problem of insufficient adsorption efficiency and stability of bisphenol A in the prior art, and achieved the effect of efficient adsorption and stable separation.
Patent Information
- Application Number
- CN202311653268.0
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2023-12-05
- Publication Date
- 2025-06-06
AI Technical Summary
The prior art is difficult to effectively remove food samples containing bisphenol A, and the traditional methods have problems such as small adsorption capacity, poor stability and difficult separation.
Ultrasonic was used to prepare magnetic covalent organic frame material (Fe3O4@TAPT-TFPA@COF), and by wrapping Fe3O4 nanospheres in a covalent organic frame, an adsorbent with high specific surface area and good magnetic responsiveness was formed.
It achieves efficient adsorption of bisphenol A and good stability separation, with the advantages of large adsorption capacity and easy separation from the sample.
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Abstract
Description
Technical Field
[0001] The invention relates to a preparation method of a magnetic organic framework material and its application in adsorbing bisphenol A, belonging to the technical field of composite material preparation and food safety detection. Background Art
[0002] Bisphenol A, also known as BPA, is an organic compound. In industry, bisphenol A is used to synthesize materials such as polycarbonate (PC) and epoxy resin. Since the 1960s, it has been used to make plastic (milk) bottles, sippy cups for infants, and the inner coating of food and beverage (milk powder) cans. BPA is everywhere, from mineral water bottles, medical devices to the inside of food packaging. Every year, 27 million tons of plastic containing BPA are produced worldwide. But BPA can also cause endocrine disorders and threaten the health of fetuses and children. Cancer and obesity caused by metabolic disorders are also believed to be related to this. The European Union believes that baby bottles containing bisphenol A can induce precocious puberty.
[0003] Magnetic covalent organic framework (MCOFs) composites are a new type of functional materials. They have the characteristics of strong magnetic properties of magnetic materials that are conducive to separation and recovery, and the characteristics of COFs such as large specific surface area, high porosity, precise molecular structure and adjustable pore size. They have attracted widespread attention in recent years. According to the composition and function of magnetic covalent organic framework materials, the reported MCOFs can be roughly divided into three categories: the first category is the original MCOFs composed of nanoparticles and COFs 2 components, with a typical structure of core@shell, and the core is generally a magnetic nanoparticle, such as Fe 3 O 4 and functionalized magnetic nanoparticles, the outer shell is a COFs layer with a porous structure. The second type is functionalized MCOFs composed of three or more components: magnetic nanoparticles, COFs and other substances (such as carbon nanotubes, graphene, β-cyclodextrin, etc.). The third type is mainly composed of iron, cobalt, nickel and their alloys and COFs. Its structure is mainly that magnetic metal and its alloy nanoparticles are embedded or dispersed in COFs to produce low-density organic-inorganic nanomagnets, thus obtaining a low-density magnetic nanocomposite material with good dispersibility.
[0004] Magnetic adsorbents are crucial in the magnetic solid phase extraction process, and the advantages of MCOFs are high specific surface area, good chemical and thermal stability, high adsorption capacity, good magnetic response, and high reusability. Therefore, MCOF is of great significance for the effective removal of BPA from food samples. Summary of the invention
[0005] The invention aims to provide a method for ultrasonically preparing a magnetic covalent organic framework and its application in adsorbing bisphenol A.
[0006] For the above purpose, the main technical solutions adopted by the present invention include: A method for ultrasonically preparing a magnetic covalent organic framework comprises the following steps: (1) Magnetic Fe 3 O 4 Preparation of nanospheres Add FeSO into a round bottom flask 4 ∙7H 2 O and FeCl 3 ∙6H 2 O, then add deionized water. Under the protection of high-purity nitrogen, the above solution is continuously stirred. After complete dissolution, the coprecipitant NH 3 ·H 2 O, and stirred continuously at 50 °C. Afterwards, the black product was collected with a strong magnet and washed five times with deionized water. 3 O 4 Vacuum dry.
[0007] (2) Magnetic covalent organic framework materials (Fe 3 O 4 Preparation of @TAPT-TFPA@COF Fe 3 O 4 Add to anhydrous ethanol and sonicate. After dissolving, add 4, 4, 4-(1, 3, 5-triazine-2,4,6-triyl)-triphenylamine and continue sonication. Then add tri-(4-formylphenyl)-amine and glacial acetic acid. Sonicate the mixed solution. Finally, wash the product with methanol and tetrahydrofuran until the supernatant is colorless and dry for later use.
[0008] The present invention also provides the application of the magnetic covalent organic framework material in adsorbing bisphenol A in water, milk, vinegar and soy sauce. The magnetic covalent organic framework material can effectively adsorb bisphenol A in the sample and has the advantages of good stability, large adsorption capacity and easy separation from the sample. BRIEF DESCRIPTION OF THE DRAWINGS
[0009] Figure 1 The magnetic covalent organic framework (Fe 3 O 4 Schematic diagram of the structure of @TAPT-TFPA@COF).
[0010] Figure 2 The Fe prepared in Example 1 3 O 4 and Fe 3 O 4 Transmission electron microscopy spectrum of @TAPT-TFPA@COF.
[0011] Figure 3 The Fe prepared in Example 13 O 4 , TAPT, TFPA and Fe 3 O 4 Infrared spectrum of @TAPT-TFPA@COF.
[0012] Figure 4 The Fe prepared in Example 1 3 O 4 and Fe 3 O 4 XRD pattern of @TAPT-TFPA@COF.
[0013] Figure 5 The Fe prepared in Example 1 3 O 4 BET spectrum of @TAPT-TFPA@COF.
[0014] Figure 6 The Fe prepared in Example 1 3 O 4 and Fe 3 O 4 VSM spectrum of @TAPT-TFPA@COF.
[0015] Figure 7 The Fe prepared in Example 1 3 O 4 XPS spectrum of @TAPT-TFPA@COF. Implementation
[0016] In order to better explain the present invention and facilitate understanding, the present invention is described in detail below through specific implementation modes in conjunction with the accompanying drawings.
[0017] Example 1 Magnetic covalent organic framework Fe 3 O 4 The preparation of @TAPT-TFPA@COF includes the following steps: (1) Magnetic Fe 3 O 4 Preparation of nanospheres Add 2.8082 g FeSO into the flask. 4 ∙7H 2 O and 5.4606 g FeCl 3 ∙6H 2 O, then add deionized water. Under the protection of high-purity nitrogen, the above solution is continuously stirred. After complete dissolution, the coprecipitant NH 3 ·H 2 O (1 mol L -1), stirred continuously at 50 °C. Afterwards, the black product was collected with a strong magnet and washed five times with deionized water. 3 O 4 Dry in vacuum at 70 °C for 6 h.
[0018] (2) Magnetic covalent organic framework materials (Fe 3 O 4 Preparation of @TAPT-TFPA@COF 40 mg Fe 3 O 4 Add to 20 mL of anhydrous ethanol, add 35 mg of 4, 4, 4-(1, 3,5-triazine-2,4,6-triyl)-triphenylamine after ultrasonic dissolution, and continue ultrasonic treatment for 20 minutes. Then add 33 mg of tri-(4-formylphenyl)-amine and 4 mL of glacial acetic acid. Ultrasonicate the mixed solution for 2 hours. Finally, wash the product with methanol and tetrahydrofuran until the supernatant is colorless and vacuum dry at 70°C for 6 hours for use.
[0019] (3) Magnetic covalent organic framework Fe 3 O 4 The synthetic route of @TAPT-TFPA@COF is as follows Figure 1 shown.
[0020] Example 2 Magnetic Covalent Organic Framework Fe 3 O 4 Characterization of @TAPT-TFPA@COF (1) Using transmission electron microscopy to study Fe 3 O 4 and magnetic covalent organic framework Fe 3 O 4 The morphology of @TAPT-TFPA@COF was characterized, such as Figure 2 As shown in a and 2b, Fe 3 O 4 The nanoparticles are spherical and about 10-20 nm in size. Figure 2 c and 2d, Fe 3 O 4 The surface of @TAPT-TFPA@COF becomes rougher, indicating that the COF layer is successfully wrapped around the Fe 3 O 4 The surface of the nanoparticles has a thickness of about 30 nm.
[0021] (2) Fourier transform infrared spectroscopy was used to analyze the Fe 3 O 4 , TAPT, TFPA and magnetic covalent organic framework Fe 3 O 4The structure of @TAPT-TFPA@COF was characterized, such as Figure 3 As shown. 632 cm -1 Corresponding to Fe 3 O 4 Fe-O stretching vibration peaks. 1360, 1500, 3320 cm -1 The peaks at 1699 cm correspond to the CN and NH stretching vibrations of TAPT. -1 The corresponding peak is the CO stretching vibration peak of TFPA. 3 O 4 @TAPT-TFPA@COF at 1580 cm -1 The C=N characteristic peak appeared at , while the CN and NH stretching vibration peaks disappeared. These results indicate that the COF shell was successfully synthesized.
[0022] (3) X-ray diffractometer was used to analyze the Fe 3 O 4 and magnetic covalent organic framework Fe 3 O 4 The crystallinity and stability of @TAPT-TFPA@COF were characterized, such as Figure 4 As shown. 3 O 4 The XRD pattern of @TAPT-TFPA@COF has diffraction peaks at 30.2°, 35.5°, 43.2°, 53.6°, 57.2° and 62.7°. From the standard spectrum (JCPDS: No.75-1610), it can be observed that the positions of these peaks are respectively consistent with those of Fe 3 O 4 The crystal planes (220), (311), (400), (422), (511) and (440) of the prepared Fe 3 O 4 @TAPT-TFPA@COF has excellent crystallinity and relatively stable crystal structure.
[0023] (4) Using BET to characterize the magnetic covalent organic framework Fe 3 O 4 The specific surface area and pore volume of @TAPT-TFPA@COF were characterized, such as Figure 5 As shown. 3 O 4 The specific surface area of @TAPT-TFPA@COF is 176.8 m 2 g -1 , pore volume is 0.23 cm³g -1 . It has a large specific surface area and is an ideal adsorbent for bisphenol A.
[0024] (5) Using VSM to treat Fe3 O 4 and magnetic covalent organic framework Fe 3 O 4 The magnetic response properties of @TAPT-TFPA@COF were characterized, such as Figure 6 As shown. 3 O 4 and Fe 3 O 4 The saturation magnetization of @TAPT-TFPA@COF is 61 emu g -1 and 43emu g -1 . Under the action of an external magnetic field, Fe 3 O 4 @TAPT-TFPA@COF can be separated by a strong magnet within 60 seconds, indicating that its magnetic properties meet the requirements of MSPE and can be used as an MSPE adsorbent.
[0025] (6) XPS analysis of the magnetic covalent organic framework Fe 3 O 4 The chemical composition of @TAPT-TFPA@COF was characterized, such as Figure 7 As shown. 3 O 4 The XPS spectrum of @TAPT-TFPA@COF shows photoelectron lines at 285, 402, 528, and 711 eV, belonging to C 1s, N 1s, O 1s, and Fe 2p, respectively. These results confirm that the magnetic covalent organic framework Fe with covalent bonds is 3 O 4 @TAPT-TFPA@COF was successfully synthesized.
[0026] Example 3 Magnetic Covalent Organic Framework (Fe 3 O 4 Application of @TAPT-TFPA@COF (1) 10 mg Fe 3 O 4 @TAPT-TFPA@COF was dispersed into 10 mL with spiked concentrations of 20, 50, and 100 μgL -1 After vortexing for 4 min, Fe 3 O 4 @TAPT-TFPA@COF. Subsequently, 1 ml of ethanol was added as a desorbent, and 1 mL of ethanol desorbent was collected after 15 min of ultrasound, and then filtered and analyzed by HPLC.
[0027] (2) The experimental results are shown in Table 1 .
[0028] (3) Result analysis: It can be concluded from Table 1 that the recovery rate of bisphenol A is 85.9%-100.1%, and RSD is <3.7%, which shows that this method has a good recovery rate and good practicality and accuracy.
[0029] The above is only a preferred embodiment of the present invention, and does not limit the present invention in other forms. Any person skilled in the art can use the above disclosed technical content to change or modify it into an equivalent embodiment with equivalent changes. However, any simple modification, equivalent change and modification made to the above embodiment according to the technical essence of the present invention without departing from the technical solution of the present invention still belongs to the protection scope of the technical solution of the present invention.
Claims
1. A method for preparing magnetic covalent organic framework materials by ultrasonic method, It is characterized in that The following steps are involved: (1) Magnetic Fe 3 O 4 Preparation of nanospheres Add FeSO into a round bottom flask 4 ∙7H 2 O and FeCl 3 ∙6H 2 O, then add deionized water. Under the protection of high-purity nitrogen, the above solution is continuously stirred. After complete dissolution, the coprecipitant NH 3 ·H 2 O with constant stirring at 50 °C. Afterwards, the black product was collected with a strong magnet and washed five times with deionized water. 3 O 4 Vacuum drying; (2) Magnetic covalent organic framework materials (Fe 3 O 4 Preparation of @TAPT-TFPA@COF Fe 3 O 4 Add to anhydrous ethanol and sonicate. After dissolving, add 4, 4, 4-(1, 3, 5-triazine-2,4,6-triyl)-triphenylamine and continue sonication. Then add tri-(4-formylphenyl)-amine and glacial acetic acid. Sonicate the mixed solution. Finally, wash the product with methanol and tetrahydrofuran until the supernatant is colorless and dry for later use.
2. The use according to claim 1, It is characterized in that In step (1), the FeSO 4 ∙7H 2 O and FeCl 3 ∙6H 2 The added amounts of O were 2.8082 g and 5.4606 g, respectively. 3 ·H 2 The concentration of O is 1 mol L -1 The drying temperature was 70°C and the drying time was 6 hours.
3. The use according to claim 1, It is characterized in that In step (2), the Fe 3 O 4 The amount added is 40 mg. The amount of anhydrous ethanol added is 20 mL. The amount of 4, 4, 4-(1, 3, 5-triazine-2,4,6-triyl)-triphenylamine added is 35 mg. The amount of tri-(4-formylphenyl)-amine added is 33 mg. The amount of glacial acetic acid added is 4 mL. The ultrasonic treatment time is 2 hours. The drying temperature is 70 ℃ and the drying time is 6 hours.
4. A magnetic covalent organic framework (Fe 3 O 4 @TAPT-TFPA@COF) in the adsorption and removal of bisphenol A. It is characterized in that The following steps are involved: (1) Prepare Fe 3 O 4 @TAPT-TFPA@COF was added to the sample solution and oscillated at room temperature for 10 min. A strong magnet was used to separate Fe 3 O 4 @TAPT-TFPA@COF, ultrasonic desorption with ethanol; (2) The samples to be tested are detected and analyzed by high performance liquid chromatography.
5. The use according to claim 4, It is characterized in that In step (1), the Fe 3 O 4 The amount of @TAPT-TFPA@COF added was 10 mg, the amount of ethanol added was 1 mL, and the ultrasonic time was 15 min.
6. The use according to claim 4, It is characterized in that In step (2), the conditions for the high performance liquid chromatography analysis are as follows: Waters Alliance HPLC system (Waters Corporation, Milford, MA 01757, USA) equipped with a 2489 detector and an Atiantis T3 (250 × 4.6 mm, 5µm) chromatographic column. The column temperature is 25 °C, and the injection volume is 20 μL. The mobile phase is methanol (A) and water (B): 0 min, 60% A; 20 min, 80% A, and the detection wavelength of bisphenol A is 280 nm.