CN115254031A - Preparation method and application of microporous network adsorption material with hollow structure - Google Patents
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Abstract
The invention relates to a preparation method and application of a microporous network adsorbing material with a hollow structure, which comprises the following steps of (a) preparing a magnetic porous organic framework material with strong adsorbability and large specific surface area by adopting an in-situ growth method; (b) Synthesizing the novel composite porous network adsorbing material with a core-shell structure through a sonogashira coupling reaction; (c) The hollow microporous network adsorbing material is prepared by a hard template method, so that selective adsorption and efficient enrichment of food and environmental pollutants are realized. The invention has the beneficial effects that: the prepared hollow microporous network adsorption material has good particle size uniformity, has obvious and efficient adsorption capacity on target pollutants, greatly improves the utilization rate of internal pores due to the hollow structure of the material, and shortens the adsorption path of a target object, thereby improving the adsorption efficiency. Meanwhile, the hollow microporous organic material enhances the hydrophobicity of the surface and the interior of the material, so that the material has higher stability in a humid environment, can better play a role in an organic solvent, and is suitable for adsorption and enrichment of various food pollutants.
Description
Technical Field
The invention belongs to the research field of hollow porous network adsorbing materials, and relates to a preparation method and application of a hollow microporous network adsorbing material.
Background
With globalization of economy, complication of industrial chain, iteration of technology, internationalization of food trade, global food safety risk is increasing. How to better ensure food safety and nutritional health and meet the increasing demands of people becomes a subject facing all countries in the world and needs to be cracked urgently. In recent years, malignant events caused by food safety problems are frequent, and serious problems of serious standard exceeding of heavy metal elements, pollution of pathogenic bacteria and microorganisms, excessive addition of food additives, chemical reagent residues, pesticide residues and the like cause a series of serious food safety problems, so that damage and loss are immeasurable. In order to meet the social requirements for food safety risk control, the development and research of technologies for rapidly, sensitively and accurately detecting chemical reagents, additives, pesticide residues and the like in food are urgent. However, although the analysis result of the conventional detection method is relatively reliable, the operation is more complicated and the sensitivity is poor, so that the development and research of related technologies capable of realizing rapid, sensitive and accurate detection are urgently needed.
The microporous organic network adsorption material is a crystalline porous material which is constructed by mutually connecting an inorganic metal center and an organic functional group through a coordination bond or an ion-coordination bond and has a regular pore channel or cavity structure. Due to the extremely high specific surface area, high chemical stability and high thermal stability, the method can realize high-efficiency enrichment of target hazards, and becomes a hot spot for research in the detection field. Due to the fact that the material diffusion efficiency is higher, the hollow structure micropore network has better adsorption performance than that of a non-hollow material. The novel hollow structure adsorption material is developed, the influence of a food matrix on a detection result is overcome, the adsorption efficiency of the material on target pollutants is improved, the enrichment and detection of the food pollutants are finally realized, and the hollow structure adsorption material has important guiding significance and social value for promoting the development of efficient detection and evaluation means and effectively supervising food pollutants.
Disclosure of Invention
Aiming at the requirements and the field blank of the research method, a microporous network adsorption material with a hollow structure is introduced. And etching the composite porous organic network material by a hard template method to obtain the adsorbing material with a hollow structure. The adsorbent has great potential as a harmful substance adsorption material due to the advantages of larger specific surface area, stronger water absorption and the like. The stable application of the complex food matrix is ensured, and the efficient enrichment and convenient control of target pollutants are realized.
The research adopts a simple hard template method to construct a novel micropore network adsorbing material with a hollow structure. The material has a typical hollow structure, and the magnetism of the material is Fe3O4The core of the microsphere is wrapped by the metal organic framework material crystal, then a microporous organic network is introduced to the surface of the metal organic framework material through sonogashira coupling reaction, and finally the magnetic metal organic framework is etched through hydrofluoric acid. And (3) enriching and determining the target pollutants in the complex matrix sample by combining analysis means such as high performance liquid phase or gas phase. The material has good enrichment capacity, and effectively simplifies the pretreatment step. More importantly, the hollow structure microporous network material obviously improves the specific surface area and the hydrophobicity of the whole adsorbent, thereby improving the adsorption efficiency on a target object, particularly greatly improving the adsorption capacity on the hydrophobic target object, and being beneficial to the practical application of the material.
The invention aims to etch a magnetic microporous organic network composite material for the first time to obtain a microporous network adsorption material with a hollow structure, introduce the material into the field of food science research, greatly improve the specific surface area of the material, and make the adsorption efficiency and repeatability more superior, realize convenient pretreatment and efficient enrichment of target pollutants, open up a new way for detection of food hazardous substances, and hopefully develop innovative and advanced food safety and nutrition analysis methods and research concepts, and have important leading significance for further and strictly monitoring and controlling the hazardous substances in food and promoting the application of advanced functional material-based analytical chemistry methodology in food safety and human health science.
The specific technical scheme provided by the invention is as follows:
the preparation and application of the microporous network adsorption material with the hollow structure comprise the following steps:
(a) Preparing a magnetic porous organic framework material with strong adsorbability and large specific surface area by adopting an in-situ growth method;
(b) Preparing a novel composite porous network adsorbing material with a core-shell structure, which has strong hydrophobicity and stable chemical properties, through a sonogashira coupling reaction;
(c) Through a hard template method, a hollow microporous network adsorbing material with stronger adsorbability and hydrophobicity and stable chemical performance is synthesized, and the high-efficiency enrichment of food pollutants is realized.
Further, the step (a) adopts an in-situ growth method, and the process for preparing the magnetic porous organic framework material with strong adsorbability and large specific surface area comprises the following steps:
(1) Magnetic Fe3O4The preparation of (1): feCl is added3·6H2O, anhydrous sodium acetate and ethylene glycol are mixed and stirred for 60 minutes, and then the mixture is transferred into a Teflon-lined hydrothermal reaction kettle and heated for 8 hours at the temperature of 200 ℃. After the reaction was cooled to room temperature, the reaction mixture was washed 4 times with ultrapure water. Followed by vacuum drying at 60 ℃ for 12 hours, and collecting the black magnetic powder product.
(2) Magnetic Fe3O4@SiO2The preparation of (1): taking 1.0g of the magnetic Fe obtained in the step (1)3O4200mL of HCl was added, sonicated for 10min, and then rinsed 3 times with ultrapure water. 80mL of ultrapure water, 320mL of ethanol and 5mL of ammonia water were added, and the mixture was subjected to ultrasonic treatment for 10min. Then 1mL TEOS was added and mechanically stirred for 12 hours. The resulting product was collected with a magnet and washed four times with ultrapure water and ethanol alternately.
(3) Magnetic Fe3O4@SiO2@UiO-66-NH2The preparation of (1): taking 150mg of the magnetic Fe obtained in the step (2)3O4@SiO2Then, 300mg of zirconium (IV) chloride, 75. Mu.L of water and 30mL of DMF were added thereto and the mixture was stirred for 15min. Then, 2-aminoterephthalic acid was added thereto and stirred to be completely dissolved. The above solution was transferred to a Teflon-lined hydrothermal reaction vessel and heated at 120 ℃ for 24 hours. Is cooled toAfter room temperature, the brown-black magnetic microspheres are collected and washed with ultrapure water for many times. Finally, the product was dried under vacuum at 60 ℃ for 12 hours.
Further, the step (1) FeCl3·6H227g of O, 57.5g of anhydrous sodium acetate and 500mL of glycol.
Further, the concentration of HCl used in the step (2) is 0.1mol/L, and the concentration of ammonia water is 25-28%.
Further, the amount of the 2-aminoterephthalic acid used in the step (3) is 235mg.
Further, the process for preparing the novel composite porous network adsorption material with the core-shell structure, which has strong hydrophobicity and stable chemical properties, through sonogashira coupling reaction in the step (b) is as follows:
taking 200mg of Fe obtained in the step (a)3O4@SiO2@UiO-66-NH2Adding 15mL of toluene, 15mL of triethylamine and a proper amount of catalyst, and carrying out ultrasonic treatment for 30min. After complete dispersion, the mixture was mechanically stirred at 90 ℃ for 30min, 50mg of tetrakis (4-ethynylphenyl) methane and 80mg of 1, 4-diiodobenzene were added, and heating was continued at 90 ℃ for 6 hours. Cooling the reaction system to room temperature, collecting the product by using a magnet, washing the product by using dichloromethane and methanol for five times, and drying the product in vacuum at 50 ℃ to obtain brownish black powder, namely the magnetic composite porous network adsorbing material Fe3O4@SiO2@UiO-66-NH2@MON。
Further, the catalyst and the amount of the catalyst were 3.4mg of bis (triphenylphosphine) palladium (II) dichloride and 1.0mg of cuprous iodide.
Further, the step (c) synthesizes the hollow microporous network adsorbing material with stronger adsorbability and hydrophobicity and stable chemical performance by a hard template method, and the process for realizing the high-efficiency enrichment of food pollutants comprises the following steps:
taking 100.0mg of Fe obtained in the step (b)3O4@SiO2@UiO-66-NH2@ MON, adding 10ml HF (5%) to react for 15min, washing with ethanol and water for five times, and vacuum drying at 50 ℃ to obtain black powder, namely the hollow-structure microporous network adsorbing material.
Further, the volume of hydrofluoric acid in the step is 10ml;
further, placing the obtained hollow microporous network adsorption material HMON in a target solution to realize the enrichment of the target;
the application of the invention is that the prepared hollow microporous network adsorption material has good particle size uniformity and specific surface area, has obvious and efficient adsorption capacity on target pollutants, and simultaneously, the hollow material has good chemical stability, can be repeatedly utilized for many times, and accords with the concept of green chemistry.
Reported porous network adsorption materials, such as metal organic framework materials, super-crosslinked polymeric materials and the like, respectively have the defects of poor stability, complex synthetic process, poor adsorption capacity and the like, and have very limited application in practice. The hollow microporous network adsorption material prepared by the invention has the advantages of high porosity, large specific surface area and good chemical stability, can fully exert the high-efficiency adsorption performance of the porous material, can ensure the stable application of the porous material in a complex food matrix, and further realizes the high-efficiency enrichment and convenient control of target pollutants.
The invention has the beneficial effects that:
(1) The microporous network adsorbing material with the hollow structure, which is prepared by the invention, has the advantages of uniform porosity, large specific surface area, stable chemical properties and the like, effectively simplifies the pretreatment step, can realize high-efficiency adsorption and enrichment of food hazardous substances, and opens up a new way for detection of the food hazardous substances.
(2) The hollow microporous network adsorption material developed by the invention is expected to expand innovative and advanced food safety and nutriology analysis methods and research concepts, and has important leading significance for further strictly monitoring and controlling hazardous substances in food and promoting the application of advanced functional material-based analytical chemistry methodology in food safety and human health science.
(3) The quantity of each substance is reasonably selected, the optimum reaction proportion and reaction conditions are obtained through detailed comparison, analysis and optimization in the experimental process, and the hollow structure microporous network adsorption material obtained through reaction has the optimum adsorption performance.
Description of the drawings:
FIG. 1: (A) Transmission electron micrographs (a, b, c) of the magnetic composite porous network adsorbent material; (d, e, f) a hollow microporous organic network material; (B) Dynamic light scattering analysis of magnetic composite porous network materials and hollow microporous organic network materials
FIG. 2: n is a radical of2An adsorption-desorption isotherm (A) a magnetic composite porous network adsorbing material; (B) a hollow microporous organic network material; (C) Comparing the particle size and the adsorption capacity of the magnetic composite porous network material and the hollow microporous organic network material; (D) The particle size and the adsorption capacity of the hollow microporous organic network material under different pH values; (E) Comparing the core volume of the magnetic composite porous network material and the hollow microporous organic network material; (F) Core diameter of magnetic composite porous network material and hollow microporous organic network material
FIG. 3: water contact angle measurement of magnetic composite porous network materials and hollow microporous organic network materials
FIG. 4: researching the adsorption kinetics of the hollow microporous organic network material (A); (B) Study of adsorption equilibrium
FIG. 5: and (4) evaluating the repeatability of the magnetic composite porous network adsorption material.
Detailed Description
In order that the above features and advantages of the present invention will be readily understood and appreciated, embodiments of the present invention will be described in further detail below with reference to the accompanying drawings.
Example 1
Preparation of hollow microporous network adsorption material
(1) An in-situ growth method is adopted to prepare the magnetic porous organic framework material with strong adsorbability and large specific surface area.
Magnetic Fe3O4The preparation of (1): 27g of FeCl3·6H2O, 57.5g of anhydrous sodium acetate and 500mL of ethylene glycol were mixed, stirred for 60 minutes, and then transferred to a Teflon-lined hydrothermal reaction vessel and heated at 200 ℃ for 8 hours. After the reaction was cooled to room temperature, the reaction mixture was washed 4 times with ultrapure water. Followed by vacuum drying at 60 ℃ for 12 hours, and collecting the black magnetic powder product.
Magnetic Fe3O4@SiO2The preparation of (1): taking 1.0g of the magnetic Fe obtained in the previous step3O4200mL of HCl (0.1 mol/L) was added, sonicated for 10min, and then rinsed 3 times with ultrapure water. 80mL of ultrapure water, 320mL of ethanol and 5mL of ammonia (25-28%) were added, and the mixture was subjected to ultrasonic treatment for 10min. 1ml of TEOS was then added and the mixture was mechanically stirred for 12 hours. The resulting product was collected with a magnet and washed four times with ultrapure water and ethanol alternately. Magnetic Fe3O4@SiO2@UiO-66-NH2The preparation of (1): taking 150mg of the magnetic Fe obtained in the previous step3O4@SiO2Then, 300mg of zirconium (IV) chloride, 75. Mu.L of water and 30mL of DMF were added thereto and the mixture was stirred for 15min. Then, 235mg of 2-aminoterephthalic acid was added thereto, and stirred until completely dissolved. The above solution was transferred to a Teflon-lined hydrothermal reaction vessel and heated at 120 ℃ for 24 hours. After cooling to room temperature, the brownish black magnetic microspheres are collected and washed with ultrapure water for many times. Finally, the product was dried under vacuum at 60 ℃ for 12 hours.
(2) The novel composite porous network adsorbing material with the core-shell structure, which is strong in hydrophobicity and stable in chemical property, is prepared through sonogashira coupling reaction.
Taking 200mg of Fe obtained in the step (1)3O4@SiO2@UiO-66-NH215mL of toluene, 15mL of triethylamine, 3.4mg of bis (triphenylphosphine) palladium (II) dichloride and 1.0mg of cuprous iodide were added, followed by sonication for 30min. After complete dispersion, the mixture was mechanically stirred at 90 ℃ for 30min, 50mg of tetrakis (4-ethynylphenyl) methane and 80mg of 1, 4-diiodobenzene were added, and heating was continued at 90 ℃ for 6 hours. Cooling the reaction system to room temperature, collecting the product by using a magnet, washing the product by using dichloromethane and methanol for five times, and drying the product in vacuum at 50 ℃ to obtain brownish black powder, namely the magnetic composite porous network adsorbing material Fe3O4@SiO2@UiO-66-NH2@MON。
(3) Through a hard template method, a hollow microporous network adsorbing material with stronger adsorbability and hydrophobicity and stable chemical performance is synthesized, and the high-efficiency enrichment of food pollutants is realized.
Taking 100.0mg of Fe obtained in the step (b)3O4@SiO2@UiO-66-NH2@ MON, reaction 1 by addition of 10ml HF (5%)5min, washing with ethanol and water for five times, and vacuum drying at 50 deg.C to obtain black powder as the hollow microporous network adsorption material
Example 2
The material obtained in the example 1 is placed in an aflatoxin B1 solution to realize the enrichment of aflatoxin B1. The quantitative detection can be carried out by combining with the high performance liquid chromatography.
Example 3
The material obtained in the example 1 is placed in an aflatoxin B2 solution to realize the enrichment of aflatoxin B2. The quantitative detection can be carried out by combining with the high performance liquid chromatography.
Example 4
The material obtained in the example 1 is placed in an aflatoxin G1 solution to realize the enrichment of aflatoxin G1. The quantitative detection can be carried out by combining with the high performance liquid chromatography.
Example 4
The material obtained in the example 1 is placed in an aflatoxin G2 solution to realize the enrichment of aflatoxin G2. The quantitative detection can be carried out by combining with the high performance liquid chromatography.
Fig. 1 is a transmission electron microscope image and dynamic light scattering analysis of the magnetic composite porous network adsorption material and the hollow microporous network adsorption material, and shows that the prepared hollow adsorption material has better particle size uniformity and size of about 200nm, and is suitable for pretreatment of food hazardous substances.
Fig. 2 is a chemical property representation of the magnetic composite porous network adsorbing material, which shows that the prepared hollow microporous network adsorbing material has good chemical stability and adsorption performance.
Fig. 3 is a hydrophobicity investigation of the magnetic composite porous network adsorption material and the hollow microporous network adsorption material, which shows that the prepared hollow microporous network adsorption material has better hydrophobicity and is suitable for application of actual samples.
Fig. 4 shows the study on the adsorption kinetics and the study on the adsorption balance of the hollow microporous network adsorption material, which shows that the prepared hollow structure network adsorption material has high-efficiency adsorption performance on a target object.
Fig. 5 is a repeatability evaluation of the hollow microporous network adsorption material, which shows that the prepared hollow microporous network adsorption material has good reusability and is suitable for application to actual samples.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and should not be taken as limiting the invention, so that any modifications, equivalents, improvements and the like, which are within the spirit and principle of the present invention, should be included in the scope of the present invention.
Claims (10)
1. The preparation method of the microporous network adsorption material with the hollow structure is characterized by comprising the following steps:
(a) Preparing a magnetic porous organic framework material with strong adsorbability and large specific surface area by adopting an in-situ growth method;
(b) Preparing a novel composite porous network adsorbing material with a core-shell structure, which has strong hydrophobicity and stable chemical properties, through a sonogashira coupling reaction;
(c) Through a hard template method, a hollow micropore network adsorbing material with stronger adsorbability and hydrophobicity and stable chemical property is synthesized, and the high-efficiency enrichment of food pollutants is realized.
2. The preparation method of the microporous network adsorption material with the hollow structure according to claim 1, wherein the step (a) adopts an in-situ growth method, and the preparation process of the magnetic porous organic framework material with strong adsorption and large specific surface area comprises the following steps:
(1) Magnetic Fe3O4The preparation of (1): feCl is added3·6H2Mixing O, anhydrous sodium acetate and glycol, stirring for 60 minutes, transferring to a Teflon-lined hydrothermal reaction kettle, and heating for 8 hours at 200 ℃; after the reaction is finished and cooled to room temperature, washing the reaction product for 4 times by using ultrapure water, then drying the reaction product for 12 hours in vacuum at 60 ℃, and collecting black powdery product magnetic Fe3O4；
(2) Magnetic Fe3O4@SiO2The preparation of (1): taking 1.0g of the magnetic Fe obtained in the step (1)3O4Adding 200mL of HCl, carrying out ultrasonic treatment for 10min, and then rinsing with ultrapure water3 times; adding 80mL of ultrapure water, 320mL of ethanol and 5mL of ammonia water, carrying out ultrasonic treatment for 10min, then adding 1mL of TEOS, mechanically stirring for 12 hours, collecting the obtained product by using a magnet, and alternately washing the ultrapure water and the ethanol for four times to obtain magnetic Fe3O4@SiO2；
(3) Magnetic Fe3O4@SiO2@UiO-66-NH2The preparation of (1): taking 150mg of the magnetic Fe obtained in the step (2)3O4@SiO2Adding 300mg of zirconium (IV) chloride, 75 mu L of water and 30ml of DMMF, stirring for 15min, then adding 2-aminoterephthalic acid into the mixture, and stirring until the mixture is completely dissolved; transferring the solution into a Teflon-lined hydrothermal reaction kettle, heating at 120 ℃ for 24 hours, cooling to room temperature, collecting brown-black magnetic microspheres, washing with ultrapure water for multiple times, and finally drying the product at 60 ℃ in vacuum for 12 hours to obtain Fe3O4@SiO2@UiO-66-NH2。
3. The method for preparing the microporous network adsorbing material with the hollow structure according to claim 2, wherein the FeCl obtained in the step (1)3·6H227g of O, 57.5g of anhydrous sodium acetate and 500mL of glycol.
4. The method for preparing the hollow structure microporous network adsorbing material according to claim 2, wherein the HCl concentration used in the step (2) is 0.1mol/L, and the ammonia water concentration is 25-28%.
5. The method for preparing the hollow structure microporous network adsorbing material according to claim 2, wherein the amount of the 2-aminoterephthalic acid used in the step (3) is 235mg.
6. The preparation method of the microporous network adsorption material with the hollow structure according to claim 1, wherein the step (b) is to prepare a novel composite porous network adsorption material with a core-shell structure, which has strong hydrophobicity and stable chemical properties, through a sonogashira coupling reaction:
taking 200mg of Fe obtained in the step (a)3O4@SiO2@UiO-66-NH2Adding 15mL of toluene, 15mL of triethylamine and a proper amount of catalyst, and performing ultrasonic treatment for 30min. Mechanically stirring at 90 ℃ for 30min after complete dispersion, adding 50mg of tetra (4-ethynylphenyl) methane and 80mg1, 4-diiodobenzene, continuously heating at 90 ℃ for 6 hours, cooling the reaction system to room temperature, collecting the product by using a magnet, washing the product by using dichloromethane and methanol for five times, and drying in vacuum at 50 ℃ to obtain brownish black powder, namely the magnetic composite porous network adsorbing material Fe3O4@SiO2@UiO-66-NH2@MON。
7. The preparation method of the hollow structure microporous network adsorbing material according to claim 6, wherein the catalyst is 3.4mg of bis (triphenylphosphine) palladium (II) dichloride and 1.0mg of cuprous iodide.
8. The method for preparing the hollow structure microporous network adsorbing material according to claim 1, wherein the step (c) is to synthesize the hollow microporous network adsorbing material with stronger adsorbability and hydrophobicity and stable chemical property by a hard template method, so as to realize the high-efficiency enrichment of food pollutants:
taking 100.0mg of Fe obtained in the step (b)3O4@SiO2@UiO-66-NH2And @ MON, adding 10ml of 5% HF, reacting for 15min, washing with ethanol and water for five times, and then performing vacuum drying at 50 ℃ to obtain black powder, namely the microporous network adsorbing material with the hollow structure, wherein the volume of the hydrofluoric acid is 10ml.
9. The hollow structure microporous network adsorption material obtained by the preparation method of claims 1-8 is used for enriching pollutants in food.
10. The hollow structure microporous network adsorbing material used for enriching the pollutants in the food as claimed in claim 9, is characterized in that the use method comprises the following steps: the obtained material hollow microporous network adsorption material is placed in a target solution to realize the enrichment of food pollutants.
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| CN115722202A (en) * | 2022-11-08 | 2023-03-03 | 中国科学院上海高等研究院 | Yttrium-zirconium-terephthalic acid based composite magnetic adsorption material for removing organic phosphine in water, preparation method and application thereof |
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| CN115722202A (en) * | 2022-11-08 | 2023-03-03 | 中国科学院上海高等研究院 | Yttrium-zirconium-terephthalic acid based composite magnetic adsorption material for removing organic phosphine in water, preparation method and application thereof |
| CN115722202B (en) * | 2022-11-08 | 2024-03-29 | 中国科学院上海高等研究院 | Yttrium-zirconium-terephthalic acid-based composite magnetic adsorption material for removing organic phosphine in water, preparation method and application thereof |
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