CN112679684A - Magnetic porous composite material with core-shell structure and preparation method thereof - Google Patents
Magnetic porous composite material with core-shell structure and preparation method thereof Download PDFInfo
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Abstract
The invention provides a magnetic porous composite material with a core-shell structure and a preparation method thereof3·6H2O、MnCl2·4H2Mixing O, ethylene glycol, diethylene glycol and polyvinylpyrrolidone uniformly; step 2, adding sodium acetate, uniformly mixing, carrying out hydrothermal treatment, separating a product, washing and drying to obtain magnetic microsphere powder; step 3, uniformly mixing the magnetic microsphere powder, 1,3, 5-tri (4-aminophenyl) benzene and tetrahydrofuran, and adding a tetrahydrofuran solution of 2, 5-dihydroxy-1, 4-benzenedicarboxaldehyde; and 4, carrying out heat treatment on the obtained mixed system at 50-70 ℃ for 5-7 h, washing the reaction solution, separating the product, and drying to obtain the magnetic porous composite material with the core-shell structure. The method has the advantages of strong universality, convenient operation and lower cost, and can provide convenience for the pretreatment process of the sample and the detection of trace harmful substances in food.
Description
Technical Field
The invention relates to the technical field of veterinary drug residue detection, in particular to a magnetic porous composite material with a core-shell structure and a preparation method thereof.
Background
In recent years, pork is always the first choice of people in meat products, the consumption of the pork per capita is also increased year by year, and the scale of the livestock breeding industry is also continuously expanded. However, in the process of large-scale cultivation, the cultivation environment is poor, and the problem of pathogenic bacteria infection is very likely to occur. Sulfonamides and fluoroquinolones are antibiotics commonly used in livestock breeding industry, and the drugs have good antibacterial effect, and cause drug residues even if the drugs are not used properly, so that the edible safety of consumers is influenced, and therefore, the establishment of a technology which can quickly, effectively and sensitively detect the residues of various sulfonamides and fluoroquinolones is very important.
The detection of sulfanilamide drugs and fluoroquinolone drugs in pork requires pretreatment, but the existing pretreatment methods mainly include a method of directly extracting by using an organic solvent or a method of extracting by using a solid phase, and both the methods require a large amount of organic solvents.
Disclosure of Invention
Aiming at the problems in the prior art, the invention provides the magnetic porous composite material with the core-shell structure and the preparation method thereof, which have the advantages of strong universality, high feasibility, wide adaptability, convenient operation and lower cost, and can provide convenience for the pretreatment process of samples and the detection of trace harmful substances in food.
The invention is realized by the following technical scheme:
a preparation method of a magnetic porous composite material with a core-shell structure comprises the following steps:
step 1, FeCl3·6H2O、MnCl2·4H2Mixing O, ethylene glycol, diethylene glycol and polyvinylpyrrolidone, FeCl3·6H2O、MnCl2·4H2The mass ratio of the O to the polyvinylpyrrolidone is (180-360): (66-131.9): 1000-2000, and a mixed system A is obtained;
step 2, adding sodium acetate into the mixed system A, uniformly mixing to obtain a mixed system B, carrying out hydrothermal treatment on the mixed system B to obtain a reaction liquid A, separating products in the reaction liquid A, and then sequentially washing and drying to obtain magnetic microsphere powder;
step 3, uniformly mixing the magnetic microsphere powder, 1,3, 5-tri (4-aminophenyl) benzene and tetrahydrofuran according to the proportion of 150mg (50-200) mg (15-30) mL to obtain a mixed system C, and adding a tetrahydrofuran solution of 2, 5-dihydroxy-1, 4-benzenedicarboxaldehyde into the mixed system C to obtain a mixed system D;
and 4, carrying out heat treatment on the mixed system D at 50-70 ℃ for 5-7 h to obtain a reaction liquid B, washing the reaction liquid B, separating a product in the reaction liquid B, and drying to obtain the magnetic porous composite material with the core-shell structure.
Preferably, in step 1, FeCl is first added3·6H2O and MnCl2·4H2Dissolving O in the mixed solution of ethylene glycol and diethylene glycol, and then adding polyvinylpyrrolidone into the mixed solution to dissolve to obtain a mixed system A.
Preferably, the mass ratio of the sodium acetate to the polyvinylpyrrolidone in the step 2 is (0.7-1.5): 1-2.
Preferably, in the step 2, the mixed system B is treated at 190-205 ℃ for 8-14 h.
Preferably, in the step 2, the product in the reaction solution A is separated by using a magnet and then washed with ethanol for 3-5 times.
Preferably, in step 3, the magnetic microsphere powder, 1,3, 5-tris (4-aminophenyl) benzene and tetrahydrofuran are stirred for 30-50 min at the rotation speed of 300-400 rpm in the environment of 50-70 ℃, and then the 2, 5-dihydroxy-1, 4-benzenedicarboxaldehyde is added.
Preferably, in the step 3, a tetrahydrofuran solution of 2, 5-dihydroxy-1, 4-benzenedicarboxaldehyde is added into the mixed system C at a rate of 0.1-0.4 mL/min.
Preferably, the mass ratio of the 2, 5-dihydroxy-1, 4-benzenedicarboxylic aldehyde to the 1,3, 5-tris (4-aminophenyl) benzene in the tetrahydrofuran solution of the 2, 5-dihydroxy-1, 4-benzenedicarboxylic aldehyde in the step 3 is (50-150): 70-200.
A magnetic porous composite material with a core-shell structure, which is obtained by the preparation method of the magnetic porous composite material with the core-shell structure.
Compared with the prior art, the invention has the following beneficial technical effects:
the invention relates to a preparation method of a magnetic porous composite material with a core-shell structure, which takes ferric trichloride and manganese chloride as precursors, PVP as a surfactant, a mixture of EG/DEG as a solvent and a reducing agent, sodium acetate as an electrostatic stabilizer to prevent particles from agglomerating, and the alkalinity of a reaction system can be improved after hydrolysis, so that the hydrolysis of ferric trichloride and manganese chloride to form Fe (OH)3And Mn (OH)2Finally, Fe (OH)3And Mn (OH)2Magnetic manganese ferrite (MnFe) is formed after dehydration reaction2O4) The microspheres are used as an inner core, and then a Covalent Organic framework material (CoFs for short) is coated outside the microspheres in a Covalent bond combination mode of 1,3, 5-tri (4-aminophenyl) benzene and 2, 5-dihydroxy-1, 4-benzenedicarboxaldehyde to obtain the microspheres formed by the magnetic composite material with the core-shell structure.
Drawings
FIG. 1 shows MnFe of the present invention2O4Schematic diagram of the preparation process of @ COFs.
FIG. 2 shows MnFe in example 1 of the present invention2O4Microspheres and MnFe2O4Hysteresis loops of @ COFs microspheres.
FIG. 3 shows MnFe in example 1 of the present invention2O4And (6) a morphology graph of the @ COFs microspheres.
FIG. 4 shows MnFe in example 2 of the present invention2O4And (6) a morphology graph of the @ COFs microspheres.
FIG. 5 is a schematic diagram of the magnetic solid phase extraction process in examples 1 and 2 of the present invention.
Fig. 6 is a UPLC spectrum of four sulfonamide mixed label samples in example 1 of the present invention.
Detailed Description
The present invention will now be described in further detail with reference to specific examples, which are intended to be illustrative, but not limiting, of the invention.
The invention relates to a preparation method of a magnetic porous composite material with a functionalized core-shell structure, which comprises the following steps:
step 1, preparation of manganese ferrite (MnFe)2O4) The magnetic micro-sphere is provided with a magnetic micro-sphere,
under the magnetic stirring, 180 mg-360 mg FeCl is added3·6H2O、66mg～131.9mgMnCl2·4H2Dissolving O into 20mL of mixed solution of Ethylene Glycol (EG) and diethylene glycol (DEG) with the volume ratio of (1-2) - (1-3), and magnetically stirring for 10-30 min to obtain a clear transparent solution;
adding 1.0-2.0 g of polyvinylpyrrolidone (PVP), transferring into an oil bath which is heated to 110-125 ℃ in advance, and heating for 10-15 min until the PVP is completely dissolved and is transparent; stopping heating, adding 0.7-1.5 g of sodium acetate, and magnetically stirring for 30-45 min; transferring the mixture into a 50-100 mL high-pressure reaction kettle, sealing the kettle, and placing the kettle in a drying oven to react for 8-14 h at 190-205 ℃; after the reaction is finished, cooling the reaction product to room temperature along with the furnace, separating the product by using a magnet by adopting a magnetic separation method, and washing the product for 3-5 times by using ethanol; putting the obtained black product into a vacuum drying oven at 60 ℃ for drying for 24h to obtain MnFe2O4Magnetic microsphere powder.
Experimentally, ferric chloride and manganese chloride are used as precursors, PVP acts as a surfactant, and a mixture of Ethylene Glycol (EG) and diethylene glycol (DEG) acts as both a solvent and a reducing agent. On the one hand, sodium acetate is used as an electrostatic stabilizer to prevent the particles from agglomerating, and on the other hand, the hydrolysate is alkaline and can promote the hydrolysis of ferric trichloride and manganese chloride to form Fe (OH)3And Mn(OH)2Finally, Fe (OH)3And Mn (OH)2Formation of MnFe after dehydration reaction2O4。
In addition, due to MnFe2O4The preparation of the manganese-based magnetic particles formed by the microspheres can adjust the particle size of the manganese-based magnetic particles by adjusting the volume ratio of EG to DEG in the reaction mixed liquid, so that compared with Fe-based magnetic particles, the manganese-based magnetic particles are more uniform in particle size, wider in particle size range, more regular in morphology, better in repeatability during batch production, higher in controllability of particle size and beneficial to standardized production of magnetic composite materials.
Step 2, synthesizing MnFe2O4@COFs；
Taking 150mg of MnFe2O4Putting the magnetic microsphere powder and 50-200 mg of 1,3, 5-tri (4-aminophenyl) benzene into a 200mL round-bottom flask, adding 15-30 mL of tetrahydrofuran, and mechanically stirring in a 50-70 ℃ constant-temperature water bath kettle at the rotating speed of 300-400 rpm for 30-50 min. In order to obtain a relatively uniform coating structure on the surface of the magnetic particles, 50-150 mg of 2, 5-dihydroxy-1, 4-benzenedicarboxaldehyde and 2-4 mL of tetrahydrofuran mixed solution are added at a constant speed of 0.1-0.4 mL/min, reaction is continued for 5-7 h after the addition is finished, a porous COFs layer is coated on the surface of the ferromanganese oxygen magnet magnetic particles successfully, the schematic diagram of the obtained core-shell structure is shown in figure 1, and the upper right corner is the structural formula of the core-shell structure. And after the reaction is finished, washing the reaction product for 3-5 times by using methanol or ethanol until the supernatant is colorless, and drying the product for later use after the supernatant is poured out.
Example 1
The invention relates to a preparation method of a functionalized magnetic porous composite material, which comprises the following steps:
step 1, preparation of manganese ferrite (MnFe)2O4) The magnetic micro-sphere is provided with a magnetic micro-sphere,
1a) measuring a mixed solution of 6mL of ethylene glycol and 14mL of diethylene glycol by using a measuring cylinder, and accurately weighing 360mg of FeCl by using an analytical balance3·6H2O、131.9mg MnCl2·4H2Dissolving the O in the mixed solution, placing the solution on a magnetic stirrer, and magnetically stirring for 20min until a clear transparent solution is obtained;
1b) opening the oil bath pan, and heating to 120 ℃; accurately weighing 2.0g of PVP by using an analytical balance, transferring the PVP into an oil bath at the temperature of 120 ℃, heating for 10min until the PVP is completely dissolved and is transparent, and stopping heating;
1c) accurately weighing 1.5g of sodium acetate by using an analytical balance, adding the sodium acetate into the solution, stirring the solution for 30min on a magnetic stirrer, transferring the solution into a 50mL high-pressure reaction kettle after the magnetic stirring is finished, sealing the reaction kettle, placing the reaction kettle in a constant-temperature drying oven, and reacting the solution for 10h at 205 ℃;
1d) after the reaction is finished, cooling the reaction product to room temperature along with a drying oven, and washing the reaction product for 5 times by using absolute ethyl alcohol by adopting a magnetic separation method; putting the obtained black product into a vacuum drying oven at 60 ℃ for drying for 24h to obtain MnFe2O4Magnetic microsphere powder;
step 2, synthesizing MnFe2O4@COFs：
2a) Accurately weighing 150mg MnFe by using an analytical balance2O4106mg of 1,3, 5-tri (4-aminophenyl) benzene (TAPB) is put into a 200mL round-bottom flask, 30mL of tetrahydrofuran solution is added, ultrasonic treatment is carried out for 10min, and then the mixture is put into a constant-temperature water bath kettle at 50 ℃ and mechanically stirred for 30 min;
2b) after stirring, accurately weighing 74mg of 2, 5-dihydroxy-1, 4-benzenedicarboxaldehyde (DP), dissolving with 4mL of tetrahydrofuran, adding the mixed solution at the speed of 0.4mL/min, and continuing mechanical stirring for 6h after the addition is finished;
2c) washing the mixture for several times by using methanol after stirring until the supernatant is colorless, drying the washed product, and storing the product for later use;
and 3, enriching and detecting the sulfonamide veterinary drugs in the livestock meat products:
(1) the pork sample is subjected to a sample pretreatment step according to a method reported in the literature, and 10mL of pork extract is obtained as a blank sample. (2) Preparing a mixed standard product of sulfanilamide. The sample is a mixed sample of 4 sulfanilamide standard substances, which are sulfadiazine (SDZ, 100 mu g/mL), sulfadimidine (SM2, 100 mu g/mL), sulfapyridine (SPD, 100 mu g/mL) and sulfadimidine (SM1, 100 mu g/mL). (3) Under the MSPE optimization condition, a sulfanilamide mixed standard sample (100 mu g/mL) is added into the extracting solution of the blank pork sampleMix well and add standard sample (10. mu.g/mL) as matrix. (4) Weighing 15mg of MnFe2O4The preparation method comprises the following steps of @ COFs particle powder serving as a magnetic solid-phase extraction agent is mixed with a matrix standard sample (10 mug/mL), the mixture is swirled for 20min to completely capture sulfanilamide molecules in the sample, the magnetic solid-phase extraction agent is separated from the mixture by using strong magnet, then an eluant is added to elute the sulfanilamide molecules from the magnetic composite particles, eluent is collected, concentration and filtration are carried out, chromatographic determination is carried out under the optimized condition, and the processing process is shown in figure 5. The chromatogram of 4 sulfonamides in the pork standard sample is shown in FIG. 6, and it can be seen that the MnFe is adopted2O4The components of 4 sulfanilamide standard samples in the pork standard sample treated by @ COFs can be well separated, and the peak shape is good.
MnFe shown in FIG. 22O4Microspheres and MnFe2O4Hysteresis loop of @ COFs microsphere, two kinds of microspheres (MnFe) can be seen2O4Microspheres and MnFe2O4@ COFs microspheres) without magnetic hysteresis, coercive force or remanence, both of which exhibit superparamagnetism and are easily and rapidly separated by a magnet. MnFe shown from FIG. 32O4The shape of the @ COFs microsphere shows that the particle size of the microsphere is between 120nm and 130nm, the coated COFs structure on the surface is uniform, and the thickness is between 10nm and 20 nm.
Example 2
The invention relates to a preparation method of a functionalized magnetic porous composite material, which comprises the following steps,
step 1, preparation of manganese ferrite (MnFe)2O4) The magnetic micro-sphere is provided with a magnetic micro-sphere,
1a) measuring a mixed solution of 7mlmL of ethylene glycol and 13ml of diethylene glycol by using a measuring cylinder, and accurately weighing 360mg of FeCl by using an analytical balance3·6H2O、131.9mg MnCl2·4H2Dissolving the O in the mixed solution, placing the solution on a magnetic stirrer, and magnetically stirring for 20min until a clear transparent solution is obtained;
1b) opening the oil bath pan, and heating to 120 ℃; accurately weighing 2.0g of PVP by using an analytical balance, transferring the PVP into an oil bath at the temperature of 120 ℃, heating for 10min until the PVP is completely dissolved and is transparent, and stopping heating;
1c) accurately weighing 1.5g of sodium acetate by using an analytical balance, adding the sodium acetate into the solution, stirring the solution for 30min on a magnetic stirrer, transferring the solution into a 50mL high-pressure reaction kettle after the magnetic stirring is finished, sealing the reaction kettle, placing the reaction kettle in a constant-temperature drying oven, and reacting the solution for 10h at 205 ℃;
1d) after the reaction is finished, cooling the reaction product to room temperature along with a drying oven, and washing the reaction product for 3-5 times by using absolute ethyl alcohol by adopting a magnetic separation method; putting the obtained black product into a vacuum drying oven at 60 ℃ for drying for 24h to obtain MnFe2O4Magnetic microsphere powder;
that is, the volume ratio of ethylene glycol and diethylene glycol in example 1 was 6:14 and 7:13 in example 2, and the difference in the ratio resulted in a change in the particle size of the magnetic particles, with the higher the ethylene glycol ratio, the larger the particles.
Step 2, synthesizing MnFe2O4@COFs：
2a) Accurately weighing 150mg MnFe by using an analytical balance2O4159mg of 1,3, 5-tri (4-aminophenyl) benzene (TAPB) is put into a 200mL round-bottom flask, 30mL of tetrahydrofuran solution is added, ultrasonic treatment is carried out for 10min, and then the mixture is put into a constant-temperature water bath kettle at 50 ℃ and mechanically stirred for 30 min;
2b) after stirring, accurately weighing 111mg of 2, 5-dihydroxy-1, 4-benzenedicarboxaldehyde (DP), dissolving with 4mL of tetrahydrofuran, adding the mixed solution at the speed of 0.4mL/min, and continuing mechanical stirring for 6h after the addition is finished;
2c) washing the mixture for several times by using methanol after stirring until the supernatant is colorless, drying the washed product, and storing the product for later use;
the difference in the ratio of the total amount of ligand to the amount of magnetic particles between example 1 and example 2 caused the difference in the thickness of COFs, as shown in FIG. 3, in the first example, the particle diameter is about 120-130nm, the COF thickness is about 10-20nm, as shown in FIG. 4, in the second example, the particle diameter is about 160-170nm, and the COF thickness is 30-40 nm.
Step 3, the enrichment detection of the fluoroquinolone veterinary drugs in the livestock meat products is the same as the enrichment detection operation of the sulfonamide veterinary drugs, which is the existing operation, and is not described herein again.
Example 3
The invention relates to a preparation method of a functionalized magnetic porous composite material, which comprises the following steps:
step 1, preparation of manganese ferrite (MnFe)2O4) The magnetic micro-sphere is provided with a magnetic micro-sphere,
1a) measuring a mixed solution of 6mL of ethylene glycol and 14mL of diethylene glycol by using a measuring cylinder, and accurately weighing 180mg of FeCl by using an analytical balance3·6H2O、66mg MnCl2·4H2Dissolving the O in the mixed solution, placing the solution on a magnetic stirrer, and magnetically stirring for 20min until a clear transparent solution is obtained;
1b) opening the oil bath pan, and heating to 120 ℃; accurately weighing 1.0g of PVP by using an analytical balance, transferring the PVP into an oil bath at the temperature of 120 ℃, heating for 10min until the PVP is completely dissolved and is transparent, and stopping heating;
1c) accurately weighing 0.7g of sodium acetate by using an analytical balance, adding the sodium acetate into the solution, stirring the solution for 30min on a magnetic stirrer, transferring the solution into a 50mL high-pressure reaction kettle after the magnetic stirring is finished, sealing the reaction kettle, placing the reaction kettle in a constant-temperature drying oven, and reacting the reaction kettle for 8h at 190 ℃;
1d) after the reaction is finished, cooling the reaction product to room temperature along with a drying oven, and washing the reaction product for 5 times by using absolute ethyl alcohol by adopting a magnetic separation method; putting the obtained black product into a vacuum drying oven at 60 ℃ for drying for 24h to obtain MnFe2O4Magnetic microsphere powder;
step 2, synthesizing MnFe2O4@COFs：
2a) Accurately weighing 150mg MnFe by using an analytical balance2O4Putting 74mg of 1,3, 5-tri (4-aminophenyl) benzene (TAPB) into a 200mL round-bottom flask, adding 30mL of tetrahydrofuran solution, carrying out ultrasonic treatment for 10min, and then mechanically stirring in a constant-temperature water bath kettle at 60 ℃ for 30 min;
2b) after stirring, accurately weighing 50mg of 2, 5-dihydroxy-1, 4-benzenedicarboxaldehyde (DP), dissolving with 4mL of tetrahydrofuran, adding the mixed solution at the speed of 0.1mL/min, and continuing mechanical stirring for 5h after the addition is finished;
2c) washing the mixture for several times by using methanol after stirring until the supernatant is colorless, drying the washed product, and storing the product for later use;
example 4
The invention relates to a preparation method of a functionalized magnetic porous composite material, which comprises the following steps:
step 1, preparation of manganese ferrite (MnFe)2O4) The magnetic micro-sphere is provided with a magnetic micro-sphere,
1a) measuring a mixed solution of 6mL of ethylene glycol and 14mL of diethylene glycol by using a measuring cylinder, and accurately weighing 240mg of FeCl by using an analytical balance3·6H2O、100mg MnCl2·4H2Dissolving the O in the mixed solution, placing the solution on a magnetic stirrer, and magnetically stirring for 20min until a clear transparent solution is obtained;
1b) opening the oil bath pan, and heating to 120 ℃; accurately weighing 1.5g PVP by using an analytical balance, transferring the PVP into an oil bath at the temperature of 120 ℃, heating for 10min until the PVP is completely dissolved and is transparent, and stopping heating;
1c) accurately weighing 1g of sodium acetate by using an analytical balance, adding the sodium acetate into the solution, stirring the solution for 30min on a magnetic stirrer, transferring the solution into a 50mL high-pressure reaction kettle after the magnetic stirring is finished, sealing the reaction kettle, placing the reaction kettle in a constant-temperature drying oven, and reacting for 14h at 200 ℃;
1d) after the reaction is finished, cooling the reaction product to room temperature along with a drying oven, and washing the reaction product for 5 times by using absolute ethyl alcohol by adopting a magnetic separation method; putting the obtained black product into a vacuum drying oven at 60 ℃ for drying for 24h to obtain MnFe2O4Magnetic microsphere powder;
step 2, synthesizing MnFe2O4@COFs：
2a) Accurately weighing 150mg MnFe by using an analytical balance2O4Putting 200mg of 1,3, 5-tri (4-aminophenyl) benzene (TAPB) into a 200mL round-bottom flask, adding 30mL of tetrahydrofuran solution, performing ultrasonic treatment for 10min, and mechanically stirring in a 70 ℃ constant-temperature water bath kettle for 30 min;
2b) after stirring, accurately weighing 150mg of 2, 5-dihydroxy-1, 4-benzenedicarboxaldehyde (DP), dissolving with 4mL of tetrahydrofuran, adding the mixed solution at the speed of 0.2mL/min, and continuing mechanical stirring for 7h after the addition is finished;
2c) washing the mixture for several times by using methanol after stirring until the supernatant is colorless, drying the washed product, and storing the product for later use;
according to the technical scheme, the implementation examples and the prior knowledge of the invention, the technical parameters can be properly adjusted to extract the sulfanilamide drugs and the fluoroquinolone drugs in other animal derived foods. Any insubstantial changes over the basic idea and process principle of the invention are considered to fall within the scope of the invention.
Claims (9)
1. A preparation method of a magnetic porous composite material with a core-shell structure is characterized by comprising the following steps:
step 1, FeCl3·6H2O、MnCl2·4H2Mixing O, ethylene glycol, diethylene glycol and polyvinylpyrrolidone, FeCl3·6H2O、MnCl2·4H2The mass ratio of the O to the polyvinylpyrrolidone is (180-360): (66-131.9): 1000-2000, and a mixed system A is obtained;
step 2, adding sodium acetate into the mixed system A, uniformly mixing to obtain a mixed system B, carrying out hydrothermal treatment on the mixed system B to obtain a reaction liquid A, separating products in the reaction liquid A, and then sequentially washing and drying to obtain magnetic microsphere powder;
step 3, uniformly mixing the magnetic microsphere powder, 1,3, 5-tri (4-aminophenyl) benzene and tetrahydrofuran according to the proportion of 150mg (50-200) mg (15-30) mL to obtain a mixed system C, and adding a tetrahydrofuran solution of 2, 5-dihydroxy-1, 4-benzenedicarboxaldehyde into the mixed system C to obtain a mixed system D;
and 4, carrying out heat treatment on the mixed system D at 50-70 ℃ for 5-7 h to obtain a reaction liquid B, washing the reaction liquid B, separating a product in the reaction liquid B, and drying to obtain the magnetic porous composite material with the core-shell structure.
2. The preparation method of the magnetic porous composite material with the core-shell structure according to claim 1, wherein FeCl is firstly added in step 13·6H2O and MnCl2·4H2Dissolving O in the mixed solution of ethylene glycol and diethylene glycol, and then adding polyvinylpyrrolidone into the mixed solution to dissolve to obtain a mixed system A.
3. The preparation method of the magnetic porous composite material with the core-shell structure, according to claim 1, is characterized in that the mass ratio of the sodium acetate to the polyvinylpyrrolidone in the step 2 is (0.7-1.5): (1-2).
4. The preparation method of the magnetic porous composite material with the core-shell structure according to claim 1, wherein the mixed system B is treated at 190-205 ℃ for 8-14 h in the step 2.
5. The preparation method of the magnetic porous composite material with the core-shell structure according to claim 1, wherein in the step 2, the product in the reaction solution A is separated by using a magnet and then washed with ethanol for 3-5 times.
6. The preparation method of the magnetic porous composite material with the core-shell structure according to claim 1, wherein in the step 3, the magnetic microsphere powder, the 1,3, 5-tris (4-aminophenyl) benzene and the tetrahydrofuran are stirred at the rotation speed of 300-400 rpm for 30-50 min in an environment with the temperature of 50-70 ℃, and then the 2, 5-dihydroxy-1, 4-benzenedicarboxaldehyde is added.
7. The preparation method of the magnetic porous composite material with the core-shell structure according to claim 1, wherein the tetrahydrofuran solution of 2, 5-dihydroxy-1, 4-benzenedicarboxaldehyde is added into the mixed system C in the step 3 at a rate of 0.1-0.4 mL/min.
8. The preparation method of the magnetic porous composite material with the core-shell structure, according to claim 1, is characterized in that the mass ratio of the 2, 5-dihydroxy-1, 4-benzenedicarboxaldehyde to the 1,3, 5-tris (4-aminophenyl) benzene in the tetrahydrofuran solution of the 2, 5-dihydroxy-1, 4-benzenedicarboxaldehyde in the step 3 is (50-150): (70-200).
9. A magnetic porous composite material with a core-shell structure, which is obtained by the preparation method of the magnetic porous composite material with the core-shell structure according to any one of claims 1 to 8.
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| CN113663646A (en) * | 2021-07-19 | 2021-11-19 | 中国计量大学 | Preparation method and application of wide-spectrum specific antibody modified magnetic metal organic framework material |
| CN114487083A (en) * | 2022-01-19 | 2022-05-13 | 中国地质大学（北京） | Magnetic hydroxyl nano material Fe3O4@ COFs and application thereof in sulfanilamide mass spectrometry detection field |
| CN115193417A (en) * | 2022-06-08 | 2022-10-18 | 苏州科技大学 | Lamellar covalent organic framework aerogel and preparation method and application thereof |
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