CN110665485A - Preparation method and application of magnetic covalent organic framework material - Google Patents
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Abstract
The invention relates to a preparation method and application of a magnetic covalent organic framework material, which comprises the following steps of (a) preparing ferroferric oxide Fe by means of a solvothermal method3O4Magnetic nanoparticles and surface activation; (b) in Fe3O4Coating TpBD covalent organic framework on the surface of the magnetic nanoparticle to obtain Fe3O4The @ TpBD composite material is applied to enrichment detection of food hazard factors. The invention has the beneficial effects that: successfully prepares a magnetic covalent organic framework material, has simple synthesis method and uniform shape and size of the nano composite materialThe reagent has large specific surface area and porous structure, and can be applied to the enrichment detection of various food hazard factors such as food packaging material processing aids, sulfanilamide veterinary drugs, biotoxins, endocrine disruptors and the like.
Description
Technical Field
The invention belongs to the research field of food hazard factor enrichment detection, and relates to a preparation method of a magnetic covalent organic framework material and application of the magnetic covalent organic framework material in sample pretreatment.
Background
With the rapid development of modern industry, great convenience is brought to the life of people, and meanwhile, a great number of negative effects are brought to the life of people. Industrial production produces many chemical contaminants that can come into full contact with environmental organisms, including humans, through various environmental media, such as air, soil, water, food, and the like. Whether these chemical pollutants may cause harm to the health of human beings and other organisms by interfering with the endocrine system of the organisms has caused great concern to endocrinologists, toxicologists, ecologists and the like internationally, and the harm and countermeasure to the ecological environment of the earth and the survival and health of human beings and other organisms have become important research subjects nowadays. In recent years, with the rapid increase of food supply and consumption in China, major food safety events occur frequently, and the food safety problem is more and more prominent and becomes a prominent problem in the field of public health. Due to chemical pollution of a series of food raw materials, application of antibiotics in animal husbandry and application of genetic engineering technology, food-borne diseases caused by food pollution are on the rise. In addition, the food production and processing technology is innovative and brings new harm.
At present, the food safety problem mainly focuses on the following aspects: microorganism hazard, heavy metal pollution, pesticide and veterinary drug residue, overproof additive, hazard in processing, storing and packaging, persistent organic pollutant, biotoxin and food adulteration. Therefore, to fundamentally solve the food safety problem, really realize the implementation of whole-process management and monitoring on various links of food production, processing, circulation, sale and the like, discover the food safety problem as early as possible, eliminate the food safety problem in the bud state, and urgently need to develop a new high-efficiency sample pretreatment, a new complex mixture high-resolution separation, high-selectivity and high-sensitivity detection method and an integrated rapid analysis system. Food hazards, which are generally low in food products, are micro-trace substances that are detected in samples of animal and plant materials and processed products with very complex matrices. The extremely low content, combined with the complex matrix, presents a high challenge to sample pretreatment and separation analysis. Aiming at the problems of complex matrix and low content of target detection substances of food samples, the method is particularly important for designing and synthesizing the high-efficiency sample pretreatment functional material, disclosing the interaction mechanism of the target substances and the functional material, and developing the sample pretreatment method and device with high selectivity, high enrichment efficiency and high flux.
Covalent organic framework materials (COFs) are purely organic porous materials composed of various organic building blocks linked together by reversible covalent bonds, and are lightweight and low density due to their being composed of purely organic elements C, N, O, B and the like. The organic molecular monomer forms an infinite circulation two-dimensional or three-dimensional structure through a specific continuous reaction, the product has good crystallinity, the pore channel is ordered, and the specific surface area is large. COF materials not only have the large specific surface area of typical porous materials, but are also the lightest class of rigid ordered porous materials. Compared with MOF materials combined through coordination bonds, the structural units of the COF materials are combined through covalent bonds, the structure of the MOF materials is more stable, the framework is not easy to collapse due to the influence of external conditions, and the MOF materials show more outstanding thermal stability and chemical stability. Once the new material is published, it has attracted great research interest, and scientists continue to design and develop various building elements and discover new connection ways to build more new COFs. On the other hand, people are also continuously improving the synthesis method, and searching for a milder and more time-saving synthesis method to enhance the applicability, and also searching for a suitable functional monomer to realize various functionalizations of COF materials, which has become a hot spot of recent research. The COF material is constructed through common reactions, and the reactions between single small molecules are simple, but it is not easy to form an infinite-cycle and orderly-crystal-form structure by continuously reversible reactions of the small molecules. Therefore, how to realize the preparation of the COF material is very critical, and people are continuously exploring a milder and simpler preparation method. The current methods for preparing COF materials mainly comprise a solvothermal method, an ionothermal method, a microwave method, a surface control method and a mechanochemical method.
Disclosure of Invention
In the work, ferroferric oxide nano particles are used as a magnetic core, and a covalent organic framework material is used as a functional surface to prepare the ferroferric oxide nano particle with large specific surface areaAnd magnetic covalent organic framework composite material Fe with porous structure3O4The synthesis method of @ TpBD is simple, the nano composite material has uniform shape and size, a typical core-shell structure and good chemical stability, and can be applied to enrichment detection of various food hazard factors such as food packaging material processing aids, sulfanilamide veterinary drugs, biotoxins, endocrine disruptors and the like. Compared with the traditional metal organic framework material, the magnetic covalent organic framework material prepared by the invention has better structural stability and chemical stability, can be simultaneously suitable for sample analysis of a water phase and an organic phase, and has wider application range and better repeatability of a sample pretreatment method. The specific technical scheme provided by the invention is as follows:
a preparation method of a magnetic covalent organic framework material comprises the following steps:
(a) preparation of ferroferric oxide Fe by means of solvothermal method3O4Magnetic nanoparticles and surface activation;
(b) in Fe3O4Coating TpBD covalent organic framework on the surface of the magnetic nanoparticle to obtain Fe3O4The @ TpBD composite material is applied to enrichment detection of food hazard factors.
Further, the step (a) prepares the ferroferric oxide Fe by means of a solvothermal method3O4The magnetic nanoparticles and the surface activation are carried out as follows:
(1) ferroferric oxide Fe3O4Preparing magnetic nanoparticles: accurately weighing 1g FeCl3·6H2Dissolving O in 30mL of ethylene glycol, adding anhydrous sodium acetate and 1, 6-hexamethylene diamine respectively under the condition of stirring, and fully stirring to obtain a transparent solution. Then transferring the mixture to a hydrothermal reaction kettle for reaction for 6 hours, washing the product with absolute ethyl alcohol for three times to obtain ferroferric oxide Fe3O4Magnetic nanoparticles;
(2) ferroferric oxide Fe3O4Surface activation of magnetic nanoparticles: the obtained ferroferric oxide Fe3O4Mixing and dispersing the magnetic nanoparticles and 2,4, 6-trihydroxy-1, 3, 5-benzene triformal (Tp) in 20mL of absolute ethyl alcohol, reacting for 1h at 50 ℃,washing the product with absolute ethyl alcohol for three times to obtain Fe with Tp-activated surface3O4Magnetic nanoparticles.
Further, the amount of anhydrous sodium acetate and 1, 6-hexanediamine added in step (1) were 2g and 5mL, respectively.
Further, the hydrothermal reaction temperature in the step (1) is 190 ℃.
Further, said step (2) is Fe3O4And Tp was used in an amount of 25mg and 1mmol, respectively.
Further, said step (b) is carried out in Fe3O4Coating TpBD covalent organic framework on the surface of the magnetic nanoparticle to obtain Fe3O4The process of the @ TpBD composite material applied to the enrichment detection of the food hazard factors is as follows:
(1)Fe3O4preparation of @ TpBD nano material: 20mL of absolute ethyl alcohol and Fe are sequentially added into a 100mL round-bottom flask3O4And stirring the mixture of Benzidine (BD) and Tp until the mixture is uniformly mixed, and introducing argon for 15min to remove oxygen in the reaction vessel. Heating the reaction solution to 80 ℃, refluxing and continuously stirring, and reacting for 3 hours; after magnetic separation, washing the product with water and ethanol for three times respectively, and then dispersing the product in an organic solvent, heating and refluxing for 2 hours to remove the unreacted Tp and BD; washing the obtained product with absolute ethyl alcohol, and then drying the product in vacuum for 24 hours at room temperature to obtain Fe3O4@ TpBD nanomaterial;
(2) and (3) enriching and detecting food hazard factors: using the Fe obtained above3O4And (3) adding the @ TpBD nano material serving as an adsorbent into a sample solution to be detected containing phthalic acid ester, vibrating for 30min, carrying out magnetic separation to remove supernatant, adding an eluent into the obtained mixed material to recover an object to be detected, and carrying out chromatographic determination.
Further, Fe in the step (1)3O4The addition amounts of BD, Tp were 25mg, 0.45mmol, 0.30mmol, respectively.
Further, the organic solvent used in the step (1) is N, N-dimethylformamide.
Further, the eluent used in the step (2) is methanol.
Further, the present invention is providedThe application of the Fe is prepared3O4The @ TpBD nano material is taken as a universal food matrix sample pretreatment material, and can adsorb, enrich and detect various food hazard factors by a solid phase extraction method.
The conventional magnetic porous framework material mostly takes a metal organic framework MOF as an adsorption structure, and at present, the defects of poor framework structure stability, heavy metal-containing toxic media, water resistance, acid-base corrosion resistance and the like exist, so that the application of the conventional magnetic porous framework material in pretreatment of complex sample matrixes such as food and the like is limited. COF is used as a porous framework material which takes covalent bonds as a main structural bonding mode, the structure of the COF has better chemical stability and water stability, and the COF does not contain heavy metal elements, has adjustable pore diameter and various ligands, has two-dimensional and three-dimensional structural modes, and can meet the requirements of different food substrate pretreatment applications.
The invention has the beneficial effects that:
(1) the magnetic covalent organic framework material is successfully prepared, the synthetic method is simple, the nano composite material is uniform in appearance and size, has a large specific surface area and a porous structure, and can be applied to enrichment detection of various food hazard factors such as food packaging material processing aids, sulfanilamide veterinary drugs, biotoxins, endocrine disruptors and the like.
(2) Compared with the traditional metal organic framework material, the magnetic covalent organic framework material prepared by the invention has better structural stability and chemical stability, can be simultaneously suitable for sample analysis of a water phase and an organic phase, and has wider application range and better repeatability of a sample pretreatment method.
Description of the drawings:
FIG. 1: transmission electron microscope and scanning electron microscope images of magnetic covalent organic framework material
FIG. 2: crystal structure characterization of magnetic covalent organic framework materials
FIG. 3: characterization of specific surface area of magnetic covalent organic framework materials
FIG. 4: characterization of magnetic properties of magnetic covalent organic framework materials
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
A preparation method and application of a magnetic covalent organic framework material comprise the following steps:
(1) preparation of ferroferric oxide Fe by means of solvothermal method3O4Magnetic nanoparticles and surface activation;
ferroferric oxide Fe3O4Preparing magnetic nanoparticles: accurately weighing 1g FeCl3·6H2O is dissolved in 30mL of ethylene glycol, 2g of anhydrous sodium acetate and 5mL of 1, 6-hexanediamine are added thereto, respectively, with stirring, and a clear solution is obtained after thorough stirring. Then transferring the mixture into a hydrothermal reaction kettle, reacting for 6 hours at 190 ℃, washing the product with absolute ethyl alcohol for three times to obtain ferroferric oxide Fe3O4Magnetic nanoparticles;
ferroferric oxide Fe3O4Surface activation of magnetic nanoparticles: 25mg of ferroferric oxide Fe obtained3O4Mixing and dispersing magnetic nanoparticles and 1mmol2,4, 6-trihydroxy-1, 3, 5-benzene triformal (Tp) in 20mL absolute ethyl alcohol, reacting for 1h at 50 ℃, washing the product three times by absolute ethyl alcohol to obtain Fe with Tp-activated surface3O4Magnetic nanoparticles.
(2) In Fe3O4Coating TpBD covalent organic framework on the surface of the magnetic nanoparticle to obtain Fe3O4The @ TpBD composite material is applied to enrichment detection of food hazard factors.
(1)Fe3O4Preparation of @ TpBD nano material: 20mL of absolute ethyl alcohol and 25mgFe are added into a 100mL round-bottom flask in sequence3O40.45mmol of Benzidine (BD) and 0.30mmol of Tp, stirring until the mixture is uniformly mixed, and introducing argon for 15min to remove oxygen in the reaction vessel. Heating the reaction solution to 80 ℃, refluxing and continuously stirring, and reacting for 3 hours; after magnetic separation, the product is washed with water and ethanol for three times respectively, and then is dispersed in N, N-dimethylformamide to be heated and refluxed for 2 hours to remove the unreacted Tp and BD; obtained byWashing the product with absolute ethyl alcohol, and then drying the product in vacuum for 24 hours at room temperature to obtain Fe3O4@ TpBD nanomaterial;
(2) and (3) enriching and detecting food hazard factors: using the Fe obtained above3O4And (3) adding the @ TpBD nano material serving as an adsorbent into a phthalate-containing sample solution to be tested, vibrating for 30min, carrying out magnetic separation to remove supernatant, adding methanol into the obtained mixed material to elute the substance to be tested, and carrying out chromatographic determination.
Example 2
The preparation method and the application of the magnetic covalent organic framework material are basically the same as the steps and the method in the embodiment 1, and the difference is that the applied sample solution to be detected is a sulfanilamide veterinary drug.
Example 3
The preparation method and the application of the magnetic covalent organic framework material are basically the same as the steps and the method in the embodiment 1, except that the applied sample solution to be detected is biotoxin.
Example 4
The preparation method and the application of the magnetic covalent organic framework material are basically the same as the steps and the method in the embodiment 1, and the difference is that the applied sample solution to be detected is an endocrine disruptor.
FIG. 1 is a transmission electron microscope image and a scanning electron microscope image of a magnetic covalent organic framework material, which show that the prepared framework material has good uniformity of particle size, is about 100nm in size and is suitable for being used as an adsorbing material.
FIG. 2 is a crystal structure characterization of the magnetic covalent organic framework material, which shows that the prepared nanomaterial has a uniform crystal structure and good chemical stability.
FIG. 3 is a specific surface area test of the magnetic covalent organic framework material, which shows that the prepared magnetic framework material has a larger specific surface area and is suitable for being used as an adsorbing material.
Fig. 4 is a magnetic property representation of the magnetic covalent organic framework material, which shows that the prepared nanomaterial has strong paramagnetism and can be used as an adsorption material for rapid magnetic separation.
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 (9)
1. A preparation method of a magnetic covalent organic framework material is characterized by comprising the following steps:
(a) preparation of ferroferric oxide Fe by means of solvothermal method3O4Magnetic nanoparticles and surface activation;
(b) in Fe3O4Coating TpBD covalent organic framework on the surface of the magnetic nanoparticle to obtain Fe3O4The @ TpBD composite material is applied to enrichment detection of food hazard factors.
2. The method for preparing a magnetic covalent organic framework material according to claim 1, wherein the step (a) is to prepare ferroferric oxide (Fe) by a solvothermal method3O4The magnetic nanoparticles and the surface activation are carried out as follows:
(1) ferroferric oxide Fe3O4Preparing magnetic nanoparticles: accurately weighing 1g FeCl3·6H2Dissolving O in 30mL of ethylene glycol, respectively adding anhydrous sodium acetate and 1, 6-hexanediamine under the condition of stirring, fully stirring to obtain a transparent solution, then transferring the transparent solution into a hydrothermal reaction kettle for reaction for 6 hours, and washing the product with anhydrous ethanol for three times to obtain ferroferric oxide Fe3O4Magnetic nanoparticles;
(2) ferroferric oxide Fe3O4Surface activation of magnetic nanoparticles: the obtained ferroferric oxide Fe3O4Mixing and dispersing the magnetic nanoparticles and 2,4, 6-trihydroxy-1, 3, 5-benzene triformal in 20mL of absolute ethyl alcohol, reacting for 1h at 50 ℃, washing the product three times by the absolute ethyl alcohol to obtain Fe with the surface activated by the 2,4, 6-trihydroxy-1, 3, 5-benzene triformal3O4Magnetic nanoparticles.
3. The method of claim 2, wherein the anhydrous sodium acetate and the 1, 6-hexanediamine are added in an amount of 2g and 5mL respectively in step (1).
4. The method for preparing a magnetic covalent organic framework material according to claim 2, wherein the hydrothermal reaction temperature in step (1) is 190 ℃.
5. The method of claim 2, wherein the step (2) is Fe3O4And 2,4, 6-trihydroxy-1, 3, 5-benzenetricarboxylic acid were used in an amount of 25mg and 1mmol, respectively.
6. Step (b) of claim 1 in Fe3O4Coating TpBD covalent organic framework on the surface of the magnetic nanoparticle to obtain Fe3O4The process of the @ TpBD composite material applied to the enrichment detection of the food hazard factors is as follows:
(1)Fe3O4preparation of @ TpBD nano material: 20mL of absolute ethyl alcohol and Fe are sequentially added into a 100mL round-bottom flask3O4Stirring the nano particles, the benzidine, the 2,4, 6-trihydroxy-1, 3, 5-benzene triformal until the nano particles, the benzidine and the 2,4, 6-trihydroxy-1, 3, 5-benzene triformal are uniformly mixed, and introducing argon for 15min to remove oxygen in a reaction container. Heating the reaction solution to 80 ℃, refluxing and continuously stirring, and reacting for 3 hours; after magnetic separation, the product is washed by water and ethanol for three times respectively, and then the product is dispersed in an organic solvent to be heated and refluxed for 2 hours to remove unreacted 2,4, 6-trihydroxy-1, 3, 5-benzene tricarbaldehyde and benzidine; washing the obtained product with absolute ethyl alcohol, and then drying the product in vacuum for 24 hours at room temperature to obtain Fe3O4@ TpBD nanomaterial;
(2) and (3) enriching and detecting food hazard factors: using the Fe obtained above3O4And (3) adding the @ TpBD nano material serving as an adsorbent into a sample solution to be detected containing phthalic acid ester, vibrating for 30min, carrying out magnetic separation to remove supernatant, adding an eluent into the obtained mixed material to recover an object to be detected, and carrying out chromatographic determination.
7. Fe (iii) according to claim 63O4Coating TpBD covalent organic framework on the surface of the magnetic nanoparticle to obtain Fe3O4The @ TpBD composite material is applied to enrichment detection of food hazard factors, and is characterized in that Fe in the step (1)3O4The addition amounts of benzidine BD and 2,4, 6-trihydroxy-1, 3, 5-benzenetricarboxylic acid were 25mg, 0.45mmol and 0.30mmol, respectively.
8. Fe (iii) according to claim 63O4Coating TpBD covalent organic framework on the surface of the magnetic nanoparticle to obtain Fe3O4The @ TpBD composite material is applied to enrichment detection of food hazard factors, and is characterized in that the organic solvent used in the step (1) is N, N-dimethylformamide.
9. Fe (iii) according to claim 63O4Coating TpBD covalent organic framework on the surface of the magnetic nanoparticle to obtain Fe3O4The @ TpBD composite material is applied to enrichment detection of food hazard factors, and is characterized in that the eluent used in the step (2) is methanol.
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