CN112429800B - Magnetic nano functional material and synthetic method and application thereof - Google Patents

Magnetic nano functional material and synthetic method and application thereof Download PDF

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CN112429800B
CN112429800B CN202011279144.7A CN202011279144A CN112429800B CN 112429800 B CN112429800 B CN 112429800B CN 202011279144 A CN202011279144 A CN 202011279144A CN 112429800 B CN112429800 B CN 112429800B
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magnetic
perfluoropolyether
magnetic nanoparticles
magnetic nano
functional material
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CN112429800A (en
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邹伟
向佳
罗义
陈立义
郑汶江
刘波
颜杰
杨虎
李颜利
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Zhonghao Chenguang Research Institute of Chemical Industry Co Ltd
Sichuan University of Science and Engineering
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Zhonghao Chenguang Research Institute of Chemical Industry Co Ltd
Sichuan University of Science and Engineering
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Abstract

The invention discloses a magnetic nanometer functional material and a synthesis method and application thereof. The invention adopts perfluoropolyether chain with stronger affinity with the short carbon chain fluoroalkyl compound as the identification group in the magnetic material, and selects the strong magnetic nano-particles to quickly separate the material from an aqueous solution system, and the magnetic nano-functional material can efficiently identify the short carbon chain perfluoroalkyl substance and can be simply, conveniently and quickly separated from the aqueous solution.

Description

Magnetic nano functional material and synthetic method and application thereof
Technical Field
The invention relates to the technical field of sewage treatment, in particular to a magnetic nano functional material and a synthetic method and application thereof.
Background
The perfluoroalkyl compounds are widely applied to the industries of chemical industry, paper making, electronics and the like due to excellent performance, and mainly comprise long-carbon-chain perfluoroalkyl compounds (the length of a carbon chain is more than 7) and short-carbon-chain perfluoroalkyl compounds (the length of a carbon chain is less than 7), wherein common long-carbon-chain perfluoroalkyl compounds comprise perfluorooctanoic acid (PFOA), perfluorooctylsulfonic acid (PFOS) and the like, and the compounds can induce various diseases, such as: cancer, hypertension, reproductive diseases, etc. The short-carbon-chain perfluoroalkyl compounds comprise trifluoroacetic acid, pentafluoropropionic acid, heptafluorobutyric acid, perfluoro-2-propoxypropionic acid (GenX) and the like, have higher immediate toxicity than long-carbon-chain perfluoroalkyl compounds, can generate various symptoms in a short time after being contacted, and can bring huge damage to mucosal tissues, upper respiratory tracts, eyes and skins of human bodies.
At present, various methods for removing long carbon chain perfluoroalkyl compounds in an aqueous environment have been reported, such as ion exchange technology, and targeted capture materials with specific recognition capability designed by utilizing the affinity between fluorine substances, etc. The methods can effectively remove the long-carbon-chain perfluoroalkyl compounds in the water environment, but the methods have low removal efficiency on the short-carbon-chain perfluoroalkyl compounds in the water environment. Because the fluorocarbon chain of the short-carbon-chain perfluoroalkyl compound is very short, the affinity between the short-carbon-chain perfluoroalkyl compound and the fluorocarbon chain on the target material is greatly reduced, so that the target material has very undesirable removal effect on the short-carbon-chain perfluoroalkyl compound. Therefore, how to effectively remove the perfluoroalkyl compounds with short carbon chains in the aqueous environment has become a technical problem to be solved by those skilled in the art.
Disclosure of Invention
Aiming at the defects in the prior art, the invention aims to provide a magnetic nano functional material, a synthetic method and application thereof, so as to solve the problem that the prior art has poor effect on removing a short-carbon-chain perfluoroalkyl compound in a water environment.
In order to solve the technical problem, the invention adopts the following technical scheme:
a magnetic nano functional material is used for removing short-carbon-chain perfluoroalkyl compounds in a water environment, ferromagnetic magnetic nano particles are selected as a substrate material, a layer of inert protective layer easy to chemically modify is coated on the surface of the substrate material, and a perfluoropolyether chain and a hydrophilic group are grafted on the inert protective layer to obtain the magnetic nano functional material.
Preferably, the base material comprises Fe 3 O 4 、MnFe 2 O 4 、NiFe 2 O 4 、CoFe 2 O 4 Has a particle diameter of 5 to 100nm and a magnetic property of 70 to 150emu/g.
Preferably, the inert protective layer comprises polydopamine, siO 2 One or more of urea formaldehyde resin, melamine resin, aminophenol-formaldehyde resin and polystyrene.
Preferably, the perfluoropolyether chain includes one or more of perfluoropolyether carboxylic ethers (types d, k, y, z), perfluoropolyether acid chlorides (types d, k, y, z), perfluoropolyether acid fluorides (types d, k, y, z), perfluoropolyether amides (types d, k, y, z), perfluoropolyether monol diols (types d, k, y, z), perfluoropolyether olefins (types d, k, y, z), perfluoropolyether propylene ethers, perfluoropolyether acrylates, trimethoxy perfluoropolyether silanes, triethoxy perfluoropolyether silanes.
Preferably, the hydrophilic group comprises one or more of polyethylene glycol, poly (N-isopropylacrylamide), polyvinyl alcohol, N-dimethylformamide, hydroxyethylcellulose, polyetheramine, and cetophenoxyethylene ether.
The invention relates to a preparation method of a magnetic nano functional material, which comprises the following steps:
(1) Preparing modified magnetic nanoparticles:
dissolving magnetic nanoparticles in an organic solvent, adding dimethyl sulfoxide and dopamine hydrochloric acid, reacting for 1-12 h at 50-100 ℃, and washing with absolute ethyl alcohol to obtain modified magnetic nanoparticles; wherein the mass ratio of the dopamine hydrochloride to the magnetic nanoparticles is 1-10;
(2) Coating of an inert protective layer:
adding a Tris-buffer solution into a reactor, adding the modified magnetic nanoparticles prepared in the step (1) as a substrate material and an inert protective layer material into the reactor for heating reaction, and washing with absolute ethyl alcohol to obtain magnetic nanoparticles coated by an inert protective layer; wherein the mass ratio of the base material to the inert protective layer material is 2:1, and the reaction is carried out for 1 to 10 hours at the temperature of between 20 and 30 ℃;
(3) Modification of hydrophilic group:
placing the magnetic nanoparticles coated by the inert protective layer prepared in the step (2) into a reactor, adding a Tris-buffer solution, adding a hydrophilic group, and reacting at a certain temperature to obtain hydrophilic modified magnetic nanoparticles; wherein, the mass ratio of the magnetic nano-particles coated by the inert protective layer to the hydrophilic groups is 1:2, and the reaction is carried out for 20 to 28 hours at the temperature of between 20 and 30 ℃;
(4) Modification of fluorocarbon chains:
placing the hydrophilic modified magnetic nanoparticles prepared in the step (3) into a reactor, adding an organic solvent, performing ultrasonic dispersion, then adding perfluoropolyether chains with different structures and an auxiliary agent (a catalyst or an acid-binding agent), stirring, heating, reacting, washing with absolute ethyl alcohol, and drying to obtain the magnetic nano material; wherein the mass ratio of the base material to the perfluoropolyether chain is 1:4.
Preferably, the synthesis of the strongly magnetic nanoparticles in step (1) comprises the following steps: selecting a corresponding substrate material, adding the substrate material into a reactor, taking octyl ether as a solvent, stirring at room temperature, adding oleic acid, oleylamine and 1,2-hexadecyl glycol, heating and stirring, continuing to heat to 100 ℃, stirring and preserving heat, raising the temperature to 200 ℃ at the speed of 4 ℃/min, continuing to preserve heat for a period of time, raising the temperature to 300 ℃ at the speed of 4 ℃/min, continuing to preserve heat for a period of time, cooling to room temperature, adding absolute ethyl alcohol and cyclohexane, washing for multiple times by using absolute ethyl alcohol after centrifugal separation, and obtaining the ferromagnetic nanoparticles.
Preferably, the product prepared in each step is stored at-10 to 10 ℃.
Preferably, the prepared magnetic nano material is screened by the following steps: and placing the synthesized magnetic nano material in deionized water, sealing, performing ultrasonic dispersion for 2-60 min, placing the magnetic nano material on a neodymium magnet, standing for 2-60 min, and cleaning particles suspended in the solution to obtain the magnetic nano material with strong magnetism and better coating after screening.
The application of the magnetic nano functional material in removing the short-carbon-chain perfluoroalkyl compound in the water environment is disclosed, and the magnetic nano functional material is obtained by the preparation method disclosed by the invention, and specifically comprises the following steps:
placing the prepared magnetic nano functional material in simulated wastewater containing a short-carbon-chain perfluoroalkyl compound, dispersing for 10-120 min by using ultrasonic, sealing, placing in a constant-temperature oscillator, and oscillating for 20-120 min under constant temperature; and then placing the mixture on a neodymium magnet and standing for 10-200 s, taking supernatant and filtering the supernatant by using a filter membrane, and then measuring the removal rate of the short-carbon-chain perfluoroalkyl compound.
Compared with the prior art, the invention has the following beneficial effects:
1. the method selects the magnetic nanoparticles with strong magnetism and good biocompatibility as the substrate material, the material is a superparamagnetic material, has strong coercive force, and can achieve the effect of rapid separation under the action of a magnetic field; the magnetic particles are spherical and have small particle size, so that the particles can provide larger specific surface area. The metal magnetic material has great surface energy, so that an inert protective layer is easily coated on the surface of the metal magnetic material, the selected inert protective layer has a plurality of active sites, the inert protective layer can be modified with perfluoropolyether chains and hydrophilic groups through simple chemical reaction, on one hand, the dispersibility of magnetic nanoparticles in water can be improved through the hydrophilic groups, so that the material is better dispersed in a water environment, on the other hand, the modified perfluoropolyether chains are used for identifying the short-carbon-chain perfluoroalkyl compounds in the water environment and are firmly combined with the short-carbon-chain perfluoroalkyl compounds, and therefore, the short-carbon-chain perfluoroalkyl compounds are removed from the water environment under the action of a magnetic field.
2. The perfluoropolyether chain selected by the invention has a good recognition effect on the short-carbon-chain perfluoroalkyl compound, can be rapidly captured and firmly combined with the short-carbon-chain perfluoroalkyl compound, and compared with the existing targeted capture material, the magnetic nanoparticle has the advantages of fast recognition, high removal rate and fast separation.
Drawings
Fig. 1 is a TEM image of magnetic nanoparticles (a) and coated poly-dopamine (b) synthesized by the present invention.
Fig. 2 is an XPS diagram of the magnetic nanomaterial synthesized in example 1 in the method for synthesizing a magnetic nano-functional material according to the present invention.
FIG. 3 is a Fourier infrared spectrum of the magnetic nano-functional material synthesized in example 1.
FIG. 4 is a graph showing the separation effect of example 9.
FIG. 5 shows poly (ethylene glycol) chains and y-type perfluoropolyether chains modified with poly (dopamine) at D 2 Of trifluoroacetic acid in O 19 F-NMR chart (refer to the preparation of example 1 without addition of magnetic nanomaterial).
FIG. 6 shows poly (dopamine) -modified polyethylene glycol chains and y-type perfluoropolyether chains at D 2 For heptafluorobutyric acid in O 19 F-NMR chart (refer to the preparation of example 1 without addition of magnetic nanomaterial).
FIG. 7 shows poly (dopamine) -modified polyethylene glycol chains and y-type perfluoropolyether chains at D 2 For GenX in O 19 F-NMR chart (refer to the preparation of example 1 without addition of magnetic nanomaterial).
FIG. 8 shows the removal rate of the material synthesized in example 1 for four short-fluorine-chain perfluoroalkyl species.
Detailed Description
The invention will be further explained with reference to the drawings and the embodiments.
1. Magnetic nano functional material
The magnetic nano functional material is used for removing short-carbon-chain perfluoroalkyl compounds in a water environment, ferromagnetic magnetic nano particles are selected as a substrate material, an inert protective layer which is easy to chemically modify is coated on the surface of the substrate material, and a perfluoropolyether chain and a hydrophilic group are grafted on the inert protective layer to obtain the magnetic nano material.
Wherein the base material comprises Fe 3 O 4 、MnFe 2 O 4 、NiFe 2 O 4 、CoFe 2 O 4 Has a particle diameter of 5 to 100nm and a magnetic property of 70 to 150emu/g. The substrate material is a superparamagnetic material and has good coercive force, the substrate material can be quickly magnetized to show magnetism under the action of an external magnetic field, and the magnetism disappears immediately after the external magnetic field is removed, so that the prepared magnetic nano functional material can be quickly separated from a water body under the action of the magnetic field after the capture of the short-carbon-chain perfluoroalkyl compound is completed, and the residue of the magnetic nano material in the water body is avoided. Moreover, the material has larger surface energy, and an inert protective layer is easily coated on the surface of the material.
The inert protective layer comprises polydopamine and SiO 2 One or more of urea formaldehyde resin, melamine resin, aminophenol-formaldehyde resin and polystyrene. The specific surface area of the substrate material is increased through the inert protective layer, so that more groups can be modified to capture the short-carbon-chain perfluoroalkyl compound.
The perfluoropolyether chain includes one or more of perfluoropolyether carboxylic ethers (types d, k, y, z), perfluoropolyether acid chlorides (types d, k, y, z), perfluoropolyether acid fluorides (types d, k, y, z), perfluoropolyether amides (types d, k, y, z), perfluoropolyether monoalcohols or diols (types d, k, y, z), perfluoropolyether olefins (types d, k, y, z), perfluoropolyether allyl ethers, perfluoropolyether acrylates, trimethoxy perfluoropolyether silanes, triethoxy perfluoropolyether silanes.
The hydrophilic group comprises one or more of polyethylene glycol, poly (N-isopropylacrylamide), polyvinyl alcohol, N-dimethylformamide, hydroxyethyl cellulose and polyether amine.
Table 1 composition of magnetic nano-functional materials described in examples 1-10
Figure BDA0002780145650000041
Figure BDA0002780145650000051
Subsequently, TEM, XPS and infrared spectroscopy tests are performed on the magnetic nanoparticles prepared in example 1, and specific data are shown in fig. 1, fig. 2 and fig. 3, and comparison analysis of the spectra shows that polydopamine is successfully coated on the surface of the magnetic material, and XPS data shows that the peak of F1s is very obvious when the fluorine-carbon bond is modified, so that it can be determined that the fluorine-carbon bond is successfully modified on the surface of the magnetic material. Then, the PEG chain modified magnetic material is obtained by infrared spectrum analysis at 1077cm -1 The peak shows the characteristic peak of ether bond, and the data proves that PEG chain has been successfully modified on the surface of the magnetic nano-particle. 0.5g of the prepared magnetic nanoparticles were dispersed in deionized water (FIG. 4) and placed next to the neodymium magnet, and only 15 seconds was required for the magnetic material to exhibit good separation.
Followed by subjecting trifluoroacetic acid, pentafluoropropionic acid, heptafluorobutyric acid and GenX to a reaction using PDA/PEG/y-PFPE microparticles 19 F-NMR test (FIGS. 5, 6, 7) since the particles modified with perfluoropolyether chains have good affinity for short-chain perfluoroalkyl species-CF after contact with the trapping material 3 Is shifted towards the high field. Therefore, the magnetic nanoparticles designed based on the method have good application prospect in removing short-chain fluorocarbon surfactants in water environment.
2. Preparation method of magnetic nano functional material
The method for preparing the magnetic nano functional material comprises the following steps:
(1) Preparing modified magnetic nanoparticles:
dissolving magnetic nanoparticles in an organic solvent, adding dimethyl sulfoxide and dopamine hydrochloric acid, reacting for 1-12 h at 50-100 ℃, and washing with absolute ethyl alcohol to obtain modified magnetic nanoparticles; wherein the mass ratio of the dopamine hydrochloride to the magnetic nanoparticles is 1-10;
(2) Coating of an inert protective layer:
adding a Tris-buffer solution into a reactor, adding the modified magnetic nanoparticles prepared in the step (1) as a substrate material and an inert protective layer material into the reactor for heating reaction, and washing with absolute ethyl alcohol to obtain magnetic nanoparticles coated by the inert protective layer; wherein the mass ratio of the base material to the inert protective layer material is 2:1, and the reaction is carried out for 1 to 10 hours at the temperature of between 20 and 30 ℃;
(3) Modification of hydrophilic groups:
placing the magnetic nanoparticles coated by the inert protective layer prepared in the step (2) into a reactor, adding a Tris-buffer solution, adding a hydrophilic group, and reacting at a certain temperature to obtain hydrophilic modified magnetic nanoparticles; wherein, the mass ratio of the magnetic nano-particles coated by the inert protective layer to the hydrophilic groups is 1:2, and the reaction is carried out for 20 to 28 hours at the temperature of 20 to 30 ℃;
(4) Modification of fluorocarbon chains:
placing the hydrophilic modified magnetic nanoparticles prepared in the step (3) into a reactor, adding an organic solvent, performing ultrasonic dispersion, then adding perfluoropolyether chains with different structures and an auxiliary agent (a catalyst or an acid-binding agent), stirring, heating, reacting, washing with absolute ethyl alcohol, and drying to obtain the magnetic nanomaterial; wherein the mass ratio of the base material to the perfluoropolyether chain is 1:4.
With example 1Fe 3 O 4 @ PDA/PEG/y-PFPE is taken as an example, and the specific steps are as follows:
(1) Ferromagnetic Fe 3 O 4 Synthesis of nanoparticles
A100 mL three-neck flask was charged with ferric trichloride (10 mmol), manganese dichloride (5 mmol) and octyl ether (30 mL) as a solvent, stirred at room temperature for 30min, then added with oleic acid (30 mmol), oleylamine (30 mmol) and 1,2-hexadecyldiol (50 mmol), and stirred at 50 ℃ under nitrogen for 10min. Then adjusting the temperature to 100 ℃, stirring for 3h, and then stirring for 4 ℃ min -1 The temperature was raised to 200 ℃ and stirring was continued at this temperature for 5h. Followed by 4 ℃ min -1 At a rate to raise the temperature to 300 c, and thereafter thereStirring was continued for 1h at temperature. Then removing heat source, and when the temperature is cooled to room temperature, adding 50mL anhydrous ethanol and 5mL cyclohexane at 10000r min -1 Centrifuging for 10min, washing with anhydrous ethanol for 6 times, and mixing the obtained MnFe 2 O 4 The magnetic nanoparticles were added to cyclohexane and stored at 4 ℃.
(2)MnFe 2 O 4 Hydrophilic modification of magnetic nanoparticles
MnFe synthesized in the step (1) 2 O 4 The magnetic nanoparticles were placed in a three-necked flask, 50mL of thionyl chloride was added, then 30mmol of dopamine hydrochloric acid and 30mL of deionized water were added, and then the reaction was carried out for 12h under nitrogen protection and protected from light. The obtained hydrophilic modified MnFe 2 O 4 The magnetic nanoparticles were separated on a neodymium magnet and washed 6 times with 95% ethanol, followed by drying the black magnetic nanoparticles at 40 ℃ for 8h and storing the product in a drying cabinet at 4 ℃.
(3) Coating of polydopamine
Taking 1g of the hydrophilic modified MnFe obtained in the step (2) 2 O 4 Adding magnetic nanoparticles into a 100mL three-neck flask, adding 50mL Tris-buffer solution, performing ultrasonic dispersion for 30min, placing the mixture in a constant temperature tank at 25 ℃, stirring for 30min, adding 30mmol dopamine hydrochloric acid, reacting for 3h under the condition of introducing oxygen, washing the obtained product for 6 times by using 95% ethanol, then performing vacuum drying at 40 ℃ for 12h, and placing the product in a drying oven for storage at 4 ℃.
(4) Modification of polyethylene glycol chains
Taking 0.3g of MnFe synthesized in the step (3) 2 O 4 The @ PDA magnetic nanoparticles are placed in a 100mL three-neck flask, 50mL Tris-buffer solution is added, then 0.6g aminopolyethylene glycol (M = 1000) is added, and the reaction is carried out for 24h at 25 ℃, so as to finally obtain MnFe 2 O 4 @ PDA/PEG functional magnetic nanoparticles. The material was then washed 6 times with 95% ethanol, then dried under vacuum at 40 ℃ for 12h, and the product was stored in a drying cabinet at 4 ℃.
(5) Modification of fluorocarbon chains
Taking 0.5g of MnFe synthesized in the step (4) 2 O 4 @PDA/PEGPlacing the magnetic nanoparticles into a 100mL flask, adding 50mL dichloromethane, then ultrasonically dispersing the mixed solution for 10min, then adding 10mmol y-type perfluoropolyether carboxylic acid and 5mmol pyridine, reacting for 12h at 45 ℃ under the protection of nitrogen, and then obtaining MnFe 2 O 4 @ PDA/PEG/y-PFPE magnetic nanoparticles. The material was then washed 6 times with 95% ethanol, then dried under vacuum at 40 ℃ for 12h, and the product was stored in a drying cabinet at 4 ℃.
Example 2 preparation of Fe 3 O 4 @SiO 2 /PEG/y-PFPE
Using ferromagnetic Fe 3 O 4 Nanoparticles coated with silicon dioxide (SiO) 2 ) As a substrate material, a polyethylene glycol chain and a y-type perfluoropolyether chain are modified on the surface of the substrate material to prepare the magnetic nano functional material. The method comprises the following specific steps:
(1) Ferromagnetic Fe 3 O 4 Synthesis of nanoparticles
Ferric trichloride (10 mmol) was added to a 100mL three-necked flask, and octyl ether (30 mL) was used as a solvent, and after stirring at room temperature for 30min, oleic acid (30 mmol), oleylamine (30 mmol), and 1,2-hexadecyldiol (50 mmol) were added, and the mixture was stirred at 50 ℃ for 10min under nitrogen protection. Then adjusting the temperature to 100 ℃, stirring for 3h, and then stirring for 4 ℃ min -1 The temperature was raised to 200 ℃ and stirring was continued at this temperature for 5h. Followed by 4 ℃ min -1 The temperature was raised to 300 ℃ and stirring was continued at this temperature for 1h. Then removing heat source, and adding 50mL of anhydrous ethanol and 5mL of cyclohexane when the temperature is cooled to room temperature at 10000r min -1 Centrifuging for 10min, washing with anhydrous ethanol for 6 times, and collecting Fe 3 O 4 The magnetic nanoparticles were added to cyclohexane and stored at 4 ℃.
(2)Fe 3 O 4 Hydrophilic modification of magnetic nanoparticles
Mixing the Fe synthesized in the step (1) 3 O 4 The magnetic nanoparticles were placed in a three-necked flask, 50mL of thionyl chloride was added, then 30mmol of dopamine hydrochloric acid and 30mL of deionized water were added, and then the reaction was carried out for 12h under nitrogen protection and protected from light. The hydrophilic modified Fe obtained 3 O 4 The magnetic nanoparticles were separated on a neodymium magnet and washed 6 times with 95% ethanol, followed by drying the black magnetic nanoparticles at 40 ℃ for 8h and storing the product in a drying cabinet at 4 ℃.
(3)SiO 2 Is coated with
Taking 1g of the hydrophilically modified Fe obtained in the step (2) 3 O 4 Adding magnetic nanoparticles into a 100mL three-neck flask, adding 60mL ethanol, 5mL ammonia water, stirring for 30min at 40 ℃, then adding 3mL tetraethyl orthosilicate, stirring for 30min, then continuing to react with 0.5mL 3-aminopropyltrimethoxysilane for 1h, washing the obtained product with 95% ethanol for 6 times, then drying in vacuum at 40 ℃ for 8h, and placing the product in a drying oven for storage at 4 ℃. To obtain Fe 3 O 4 @SiO 2 -NH 2 Magnetic nanomaterials.
(4) Modification of polyethylene glycol
Taking 0.3g of Fe synthesized in the step (3) 3 O 4 @SiO 2 -NH 2 The magnetic nanoparticles were placed in a 100mL three-necked flask, 50mL of dichloromethane was added, followed by 0.6g of polyethylene glycol (M = 2000), 200mL of thionyl chloride and 0.2mL of pyridine, and reacted at 45 ℃ for 3h to obtain MnFe 2 O 4 @SiO 2 -NH-PEG functional magnetic nanoparticles. The material was then washed 6 times with 95% ethanol, then dried under vacuum at 40 ℃ for 8h, and the product was stored in a drying cabinet at 4 ℃.
(5) Modification of fluorocarbon chains
Taking 0.5g of Fe synthesized in the step (4) 3 O 4 @SiO 2 Placing the-NH-PEG magnetic nanoparticles into a 100mL flask, adding 50mL dichloromethane, then carrying out ultrasonic dispersion on the mixed solution for 10min, then adding 10mmol y-type perfluoropolyether carboxylic acid and 0.5mL pyridine, and reacting at 45 ℃ for 3h under the protection of nitrogen, and then obtaining Fe 3 O 4 @SiO 2 -N-PEG/y-PFPE magnetic nanoparticles. The material was then washed 6 times with 95% ethanol, then dried under vacuum at 40 ℃ for 8h, and the product was stored in a drying cabinet at 4 ℃.
Example 3 preparation of Fe 3 O 4 @PS/PEG/y-PFPE
By using strong magnetismSexual Fe 3 O 4 The surface of the nano-particle is coated with Polystyrene (PS) as a substrate material, and then the surface of the nano-particle is modified with a polyethylene glycol chain and a y-type perfluoropolyether chain to prepare the magnetic nano-functional material. The steps (1) and (2) are the same as the embodiment 2, and the following specific steps are as follows:
(3) Coating of polystyrene
Taking 1g of the hydrophilic modified Fe obtained in the step (2) 3 O 4 Adding the magnetic nanoparticles into a 250mL three-neck flask, adding 100mL ethanol, performing ultrasonic dispersion for 10min, sequentially adding 0.5g of styrene and 0.01g of initiator azobisisobutyronitrile, and reacting at 70 ℃ for 5h. The resulting product was washed 6 times with 95% ethanol and then dried under vacuum at 40 ℃ for 8h to give Fe 3 O 4 @ PS magnetic nanoparticles, and then the product was placed in a dry box for storage at 4 ℃.
(4) Modification of polyethylene glycol
Taking 0.3g of Fe synthesized in the step (3) 3 O 4 @ PS magnetic nanoparticles were placed in a 100mL three-necked flask, 50mL of dichloromethane was added, followed by 0.6g of chlorinated polyethylene glycol (M = 2000), and reacted at 25 ℃ for 24h to give Fe 3 O 4 @ PS/PEG functional magnetic nanoparticles. The material was then washed 6 times with 95% ethanol, then dried under vacuum at 40 ℃ for 8h, and the product was stored in a drying cabinet at 4 ℃.
(5) Modification of fluorine carbon bonds
Taking 0.5g of Fe synthesized in the step (4) 3 O 4 @ PS/PEG magnetic nanoparticles are placed in a 100mL flask, 50mL of dichloromethane is added, then the mixed solution is subjected to ultrasonic dispersion for 10min, then 10mmol of y-type perfluoropolyether carboxylic acid and 0.5mL of pyridine are added, and the mixture reacts at 45 ℃ for 12h under the nitrogen protection atmosphere, so that Fe is obtained 3 O 4 @ PS/PEG/y-PFPE magnetic nanoparticles. The material was then washed 6 times with 95% ethanol, then dried under vacuum at 40 ℃ for 8h, and the product was stored in a drying cabinet at 4 ℃.
Example 4 preparation of Fe 3 O 4 @PDA/PVA/y-PFPE
Using ferromagnetic Fe 3 O 4 Nanoparticles coated with polydopamine as substrateAnd then modifying a polyvinyl alcohol chain and a y-type perfluoropolyether chain on the surface of the material to prepare the magnetic nano functional material. The steps (1), (2) and (3) are the same as the embodiment 2, and the following steps are as follows:
(4) Modification of polyvinyl alcohol
Taking 0.3g of Fe synthesized in the step (3) 3 O 4 @ PDA magnetic nanoparticles are placed in a 100mL three-neck flask, 50mL Tris-buffer solution is added, 2g amino polyvinyl alcohol (M = 20000) is added, and the reaction is carried out for 24h at 25 ℃, so that Fe is finally obtained 3 O 4 @ PDA/PVA functional magnetic nanoparticles. The material was then washed 6 times with 95% ethanol, then dried under vacuum at 40 ℃ for 12h, and the product was stored in a drying cabinet at 4 ℃.
(5) Modification of fluorine carbon bond
Taking 0.5g of Fe synthesized in the step (4) 3 O 4 @ PDA/PEG magnetic nanoparticles are placed in a 100mL flask, 50mL dichloromethane is added, then the mixed solution is subjected to ultrasonic dispersion for 10min, then 10mmol y-type perfluoropolyether carboxylic acid and 5mmol pyridine are added, and the mixture reacts at 45 ℃ for 12h under the protection of nitrogen, so that Fe is obtained 3 O 4 @ PDA/PVA/y-PFPE magnetic nanoparticles. The material was then washed 6 times with 95% ethanol, then dried under vacuum at 40 ℃ for 12h, and the product was stored in a drying cabinet at 4 ℃.
Example 5 preparation of Fe 3 O 4 @PDA/PEA/y-PFPE
Using ferromagnetic Fe 3 O 4 The surface of the nano-particle is coated with polydopamine to be used as a substrate material, and then a polyether ammonia chain and a y-type perfluoropolyether chain are modified on the surface of the nano-particle to prepare the magnetic nano-functional material. The steps (1), (2) and (3) are the same as the embodiment 2, and the following steps are as follows:
(4) Modification of polyether amino chains
Taking 0.3g of Fe synthesized in the step (3) 3 O 4 The @ PDA magnetic nanoparticles are placed in a 100mL three-neck flask, 50mL Tris-buffer solution is added, then 0.6g polyether ammonia (M = 2000) is added, and the reaction is carried out for 24h at 25 ℃, so as to finally obtain Fe 3 O 4 @ PDA/PVA functional magnetic nanoparticles. The material was then washed with 95% ethanol6 times, then vacuum drying at 40 deg.C for 12h, and storing the product in drying oven at 4 deg.C.
(5) Modification of fluorine carbon bonds
Taking 0.5g of Fe synthesized in the step (4) 3 O 4 The @ PDA/PEA magnetic nanoparticles are placed in a 100mL flask, 50mL dichloromethane is added, then the mixed solution is subjected to ultrasonic dispersion for 10min, 10mmol y-type perfluoropolyether carboxylic acid and 5mmol pyridine are added, the reaction is carried out at 45 ℃ for 12h under the nitrogen protection atmosphere, and then Fe is obtained 3 O 4 @ PDA/PEA/y-PFPE magnetic nanoparticles. The material was then washed 6 times with 95% ethanol, then dried under vacuum at 40 ℃ for 12h, and the product was stored in a drying cabinet at 4 ℃.
Example 6 preparation of Fe 3 O 4 @PDA/PEG/k-PFPE
Using ferromagnetic Fe 3 O 4 And the surface of the nano-particle is coated with polydopamine serving as a substrate material, and then a polyethylene glycol chain and a k-type perfluoropolyether chain are modified on the surface of the nano-particle to prepare the magnetic nano-functional material. The steps (1), (2), (3) and (4) are the same as the embodiment 2, and the following steps are as follows:
(5) Modification of fluorine carbon bonds
Taking 0.5g of Fe synthesized in the step (4) 3 O 4 The @ PDA/PEG magnetic nanoparticles are placed in a 100mL flask, 50mL dichloromethane is added, then the mixed solution is subjected to ultrasonic dispersion for 10min, then 10mmol k type perfluoropolyether carboxylic acid and 5mmol pyridine are added, the reaction is carried out for 12h at 45 ℃ under the nitrogen protection atmosphere, and then Fe is obtained 3 O 4 @ PDA/PEA/k-PFPE magnetic nanoparticles. The material was then washed 6 times with 95% ethanol, then dried under vacuum at 40 ℃ for 12h, and the product was stored in a drying cabinet at 4 ℃.
Example 7 preparation of Fe 3 O 4 @PDA/PEG/d-PFPE
Using ferromagnetic Fe 3 O 4 And the surface of the nano-particle is coated with polydopamine serving as a substrate material, and then a polyethylene glycol chain and a d-type perfluoropolyether chain are modified on the surface of the nano-particle to prepare the magnetic nano-functional material. The steps (1), (2), (3) and (4) are the same as the embodiment 2, and the following steps are as follows:
(5) Modification of fluorine carbon bonds
0.5g of Fe synthesized in the step (4) was taken 3 O 4 The @ PDA/PEG magnetic nanoparticles are placed in a 100mL flask, 50mL dichloromethane is added, then the mixed solution is subjected to ultrasonic dispersion for 10min, then 10mmol d-type perfluoropolyether carboxylic acid and 5mmol pyridine are added, the reaction is carried out for 12h at 45 ℃ under the nitrogen protection atmosphere, and then Fe is obtained 3 O 4 @ PDA/PEA/d-PFPE magnetic nanoparticles. The material was then washed 6 times with 95% ethanol, then dried under vacuum at 40 ℃ for 12h, and the product was stored in a drying cabinet at 4 ℃.
Example 8 preparation of Fe 3 O 4 @PDA/PEG/z-PFPE
Using ferromagnetic Fe 3 O 4 And the surface of the nano-particle is coated with polydopamine to serve as a substrate material, and then a polyethylene glycol chain and a z-type perfluoropolyether chain are modified on the surface of the nano-particle to prepare the magnetic nano-functional material. The steps (1), (2), (3) and (4) are the same as the embodiment 2, and the following steps are as follows:
(5) Modification of fluorine carbon bonds
Taking 0.5g of Fe synthesized in the step (4) 3 O 4 The @ PDA/PEG magnetic nanoparticles are placed in a 100mL flask, 50mL dichloromethane is added, then the mixed solution is subjected to ultrasonic dispersion for 10min, then 10mmol z-type perfluoropolyether carboxylic acid and 5mmol pyridine are added, the reaction is carried out for 12h at 45 ℃ under the nitrogen protection atmosphere, and then Fe is obtained 3 O 4 @ PDA/PEA/z-PFPE magnetic nanoparticles. The material was then washed 6 times with 95% ethanol, then dried under vacuum at 40 ℃ for 12h, and the product was stored in a drying cabinet at 4 ℃.
Example 9 preparation of MnFe 2 O 4 @MF/HEC/y-PFPE
MnFe using strong magnetism 2 O 4 The surface of the nano-particle is coated with melamine resin as a substrate material, and then a hydroxyethyl cellulose chain and a y-type perfluoropolyether chain are modified on the surface of the nano-particle to prepare the magnetic nano-functional material. The steps (1) and (2) are the same as the embodiment 1, and the subsequent steps are as follows:
(3) Coating with melamine resin
Taking 1g of the hydrophilic modification in the step (2)MnFe (b) of 2 O 4 Adding magnetic nanoparticles into a 100mL three-neck flask, adding 0.10g of melamine, continuing stirring until the solution becomes colorless and transparent, and then adding 1mL of formaldehyde solution for dispersing for 30min; after adding 0.05mL of hydrochloric acid and continuing the reaction for 3 hours, the obtained product is washed 6 times by using 95% ethanol, then dried in vacuum at 40 ℃ for 12 hours, and placed in a drying oven for storage at 4 ℃.
(4) Modification of hydroxyethylcellulose chains
Taking 0.3g of Fe synthesized in the step (3) 3 O 4 @ MF magnetic nanoparticles were placed in a 100mL three-necked flask, 50mL of dichloromethane were added, followed by 0.6g of hydroxyethylcellulose and 0.5mL of thionyl chloride, followed by 1mL of pyridine, and reacted at 45 ℃ for 24h to give Fe 3 O 4 @ MF/HEC functional magnetic nanoparticles. The material was then washed 6 times with 95% ethanol, then dried under vacuum at 40 ℃ for 12h, and the product was stored in a drying cabinet at 4 ℃.
(5) Modification of fluorocarbon chains
Taking 0.5g of MnFe synthesized in the step (4) 2 O 4 @ MF/HEC magnetic nanoparticles are placed in a 100mL flask, 50mL dichloromethane is added, then the mixed solution is subjected to ultrasonic dispersion for 10min, then 10mmol y-type perfluoropolyether acid and 5mmol pyridine are added, the reaction is carried out for 12h at 45 ℃ in a nitrogen protection atmosphere, and then MnFe is obtained 2 O 4 @ MF/HEC/y-PFPE magnetic nanoparticles. The material was then washed 6 times with 95% ethanol, then dried under vacuum at 40 ℃ for 12h, and the product was stored in a drying cabinet at 4 ℃.
Example 10
MnFe using ferromagnetic properties 2 O 4 Nanoparticles coated with SiO on the surface 2 As a substrate material, a polyethylene glycol chain is modified on the surface of the substrate material, and then trimethoxy perfluoropolyether silane is added to modify perfluoropolyether through simple hydrolysis reaction, so that the magnetic nano functional material is prepared. The steps (1) and (2) are the same as the embodiment 1, and the subsequent steps are as follows:
(3)SiO 2 is coated with
Taking 1g of the hydrophilic modified MnFe obtained in the step (2) 2 O 4 Adding magnetic nanoparticles into a 100mL three-neck flask, adding 60mL of ethanol, 5mL of ammonia water and 1mL of deionized water, stirring for 30min at 40 ℃, adding 3mL of tetraethyl orthosilicate, stirring for 30min, then continuously reacting 0.5mL of 3-aminopropyltrimethoxysilane for 1h, washing the obtained product with 95% ethanol for 6 times, then drying in vacuum at 40 ℃ for 8h, and placing the product in a drying oven for storage at 4 ℃. Obtaining MnFe 2 O 4 @SiO 2 -NH 2 Magnetic nanomaterials.
(4) Modification of polyethylene glycol chains
Taking 0.3g of MnFe synthesized in the step (3) 2 O 4 @SiO 2 -NH 2 The magnetic nanoparticles were placed in a 100mL three-necked flask, 50mL of dichloromethane was added, followed by 0.6g of polyethylene glycol (M = 2000), 200mL of thionyl chloride and 0.2mL of pyridine, and reacted at 45 ℃ for 3h to obtain MnFe 2 O 4 @SiO 2 -NH-PEG functional magnetic nanoparticles. The material was then washed 6 times with 95% ethanol, then dried under vacuum at 40 ℃ for 8h, and the product was stored in a drying cabinet at 4 ℃
(5) Decoration of fluorocarbon structures
0.5g of Mn synthesized in step (4) was taken 2 O 4 @SiO 2 Putting the-NH-PEG magnetic nanoparticles into a 100mL flask, adding 50mL of ethanol, 0.5mL of ammonia water and 0.2mL of deionized water, then ultrasonically dispersing the mixed solution for 10min, then adding 10mmol of trimethoxy perfluoropolyether silane, and reacting at 45 ℃ for 6h to obtain the magnetic nanoparticles modified with fluorine-carbon bonds. The material was then washed 6 times with 95% ethanol, then dried under vacuum at 40 ℃ for 8h, and the product was stored in a drying cabinet at 4 ℃.
3. Application of magnetic nano functional material
And screening the prepared magnetic nano functional material, placing the synthesized magnetic nano material in deionized water, sealing, placing the magnetic nano material in a 250mL beaker, ultrasonically dispersing for 2-60 min, placing the magnetic nano material on a neodymium magnet, and cleaning particles suspended in the solution after 2-60 min to obtain the magnetic nano material which is strong in magnetism and better in coating after screening.
And (3) respectively treating simulated wastewater containing trifluoroacetic acid, pentafluoropropionic acid, heptafluorobutyric acid and GenX by using the screened magnetic nano materials, and calculating the removal rate of the trifluoroacetic acid, the pentafluoropropionic acid, the heptafluorobutyric acid and the GenX by using the formula (1).
Similarly, comparative examples 1 to 3 were prepared by the preparation method of example 1 except that the magnetic particles were modified with the long carbon chain perfluoroalkyl compound in comparative examples 1 to 3, the simulated wastewater containing trifluoroacetic acid, pentafluoropropionic acid, heptafluorobutyric acid, and GenX was treated separately, and the removal rates for trifluoroacetic acid, pentafluoropropionic acid, heptafluorobutyric acid, and GenX were calculated by the formula (1).
Figure BDA0002780145650000121
Wherein Re is the removal rate, C o Is the initial solubility of the fluorocarbon surfactant of 1ppm r Is the residual concentration of the fluorocarbon surfactant.
Comparative example 1 preparation of Fe 3 O 4 @PDA/PEG/PFOA
Using ferromagnetic Fe 3 O 4 The surface of the nano-particle is coated with polydopamine to be used as a substrate material, and then the surface of the nano-particle is modified with a polyethylene glycol chain and perfluorooctanoic acid to prepare the magnetic nano-functional material. The steps (1), (2), (3) and (4) are the same as the embodiment 2, and the following steps are as follows:
(5) Modification of fluorine carbon bonds
Taking 0.5g of Fe synthesized in the step (4) 3 O 4 The @ PDA/PEG magnetic nanoparticles are placed in a 100mL flask, 50mL dichloromethane is added, then the mixed solution is subjected to ultrasonic dispersion for 10min, 10mmol perfluorooctanoic acid and 5mmol pyridine are added, the mixture reacts at 45 ℃ for 12h under the protection of nitrogen, and then Fe is obtained 3 O 4 @ PDA/PEA/PFOA magnetic nanoparticles. The material was then washed 6 times with 95% ethanol, then dried under vacuum at 40 ℃ for 12h, and the product was stored in a drying cabinet at 4 ℃.
Comparative example 2 preparation of Fe 3 O 4 @PDA/PEG/PFOA
Using ferromagnetic Fe 3 O 4 The surface of the nano-particle is coated with polydopamine serving as a substrate material, and then a polyethylene glycol chain and perfluorooctanoyl chloride are modified on the surface of the nano-particle to prepare the magnetic nano-functional material. The steps (1), (2), (3) and (4) are the same as the embodiment 2, and the following steps are as follows:
(5) Modification of fluorine carbon bonds
Taking 0.5g of Fe synthesized in the step (4) 3 O 4 The @ PDA/PEG magnetic nanoparticles are placed in a 100mL flask, 50mL dichloromethane is added, then the mixed solution is subjected to ultrasonic dispersion for 10min, then 10mmol perfluorooctanoyl chloride and 5mmol pyridine are added, and the mixture reacts at 45 ℃ for 12h under the protection of nitrogen, so that Fe is obtained 3 O 4 @ PDA/PEA/PFOA magnetic nanoparticles. The material was then washed 6 times with 95% ethanol, then dried under vacuum at 40 ℃ for 12h, and the product was stored in a drying cabinet at 4 ℃.
Comparative example 3 preparation of Fe 3 O 4 @PDA/PEG/PFOS
Using ferromagnetic Fe 3 O 4 The surface of the nano-particle is coated with polydopamine serving as a substrate material, and then a polyethylene glycol chain and perfluorooctyl sulfonyl chloride are modified on the surface of the nano-particle to prepare the magnetic nano-functional material. The steps (1), (2), (3) and (4) are the same as the embodiment 2, and the following steps are as follows:
(5) Modification of fluorine carbon bonds
Taking 0.5g of Fe synthesized in the step (4) 3 O 4 The @ PDA/PEG magnetic nanoparticles are placed in a 100mL flask, 50mL dichloromethane is added, then the mixed solution is subjected to ultrasonic dispersion for 10min, 10mmol perfluorooctyl sulfonyl chloride and 5mmol pyridine are added, the mixture reacts at 45 ℃ for 12h under the protection of nitrogen, and then Fe is obtained 3 O 4 @ PDA/PEA/PFOS magnetic nanoparticles. The material was then washed 6 times with 95% ethanol, then dried under vacuum at 40 ℃ for 12h, and the product was stored in a drying cabinet at 4 ℃.
Using example 1 as an example, trifluoroacetic acid, pentafluoropropionic acid, heptafluorobutyric acid, and GenX were prepared as model wastewater having a concentration of 1ppm using deionized water, 10mL of the four model wastewater was sequentially placed in 4 20mL sample bottles, and 0.01g of the product prepared in example 1 was added to each sample bottlePrepared Fe 3 O 4 @ PDA/PEG/y-PFPE magnetic nano functional particles are ultrasonically dispersed for 2min, captured at 25 ℃ for 30min, and then placed on a neodymium magnet for separation. And (3) taking 0.1mL of supernatant, and testing by using LC-MS/MS (liquid chromatography-mass spectrometry), wherein the removal rates of trifluoroacetic acid, pentafluoropropionic acid, heptafluorobutyric acid and GenX are calculated to be 99.3%, 98%, 96.5% and 99.9% in sequence.
Also, the removal effect of the magnetic nanomaterial prepared in examples 2 to 10 and comparative examples 1 to 3 from simulated wastewater containing trifluoroacetic acid, pentafluoropropionic acid, heptafluorobutyric acid, and GenX by the above method is as follows.
Table 2 examples 1-8 removal of perfluoroalkyl compounds with different short carbon chains by magnetic nanomaterials
Using magnetic nano-functional materials The removal rates of trifluoroacetic acid, pentafluoropropionic acid, heptafluorobutyric acid and GenX are sequentially
Synthesized from example 1 99.3％、98％、96.5％、99.9％
Synthesis from example 2 99.5％、97.5％、97.3％、99.6％
Synthesized from example 3 99.7％、97.6％、96.8％、99.7％
Synthesis from example 4 99.5％、98.2％、97.5％、99.6％
Synthesis from example 5 99.8％、97.8％、96.9％、99.3％
Synthesized from example 6 99.7％、98.9％、97.8％、99.99％
Synthesized from example 7 99.7％、98.6％、98.2％、99.92％
Synthesized from example 8 98.9％、97.3％、96.8％、98.8％
Synthesis from example 9 97.9％、98.9％、99.3％、98.7％
Synthesis from example 10 99.5％、98.7％、98.9％、98.9％
Comparative example 1 30.5％、43.8％、42.8％、48.6％
Comparative example 2 34.2％、41.3％、43.2％、47.2％
Comparative example 3 31.2％、42.6％、43.5％、46.7％
As can be seen from the data in table 2, the magnetic particles modified by the long fluorocarbon chain compound have far less effect on removing the short fluorocarbon chain perfluoroalkyl compound than the embodiments of the present invention. The target capture material designed by depending on the affinity between fluorine substances is mainly fluorocarbon surfactants (such as PFOA and PFOS) for treating long carbon chains in water environment, and because the fluorocarbon surfactants have hydrophobic property exhibited by longer fluorocarbon chains in water, the group of the long fluorocarbon chains on the surface modification of the material by utilizing the hydrophobic property has good capture effect on the fluorocarbon chains. However, the solubility of the fluorocarbon alkyl substance with the short fluorocarbon chain in water is higher, such as trifluoroacetic acid, pentafluoropropionic acid and heptafluorobutyric acid, so that the compound can be better combined with an aqueous solution, and the compound cannot be well combined with the long-carbon-chain perfluoroalkyl compound, so that the magnetic particles modified by the long fluorocarbon chain compound have poor removal effect on the short-carbon-chain perfluoroalkyl compound. Therefore, the magnetic nano functional material prepared by adopting different fluorocarbon bonds and different hydrophilic groups has higher removal rate on trifluoroacetic acid, pentafluoropropionic acid, heptafluorobutyric acid, genX and other short-carbon-chain perfluoroalkyl substances. Therefore, the magnetic nano functional material for removing the short-chain perfluoroalkyl substances in the water environment, which is prepared by the invention, has good removal effect on the short-chain perfluoroalkyl substances and can be quickly separated from the water environment.
Finally, it should be noted that the above embodiments are only used for illustrating the technical solutions of the present invention and not for limiting the technical solutions, and those skilled in the art should understand that modifications or equivalent substitutions can be made on the technical solutions of the present invention without departing from the spirit and scope of the technical solutions, and all that should be covered by the claims of the present invention.

Claims (6)

1. A magnetic nanometer functional material is characterized in that the magnetic nanometer functional material is used for removing short-carbon-chain perfluoroalkyl compounds in a water environment, ferromagnetic magnetic nanometer particles are selected as a substrate material, a layer of inert protective layer which is easy to chemically modify is coated on the surface of the substrate material, and the magnetic nanometer functional material is obtained after a perfluoropolyether chain and a hydrophilic group are grafted on the inert protective layer;
the base material comprises Fe 3 O 4 、MnFe 2 O 4 、NiFe 2 O 4 、CoFe 2 O 4 The particle size of the magnetic material is 5 to 100nm, and the magnetism is 70 to 150 emu/g;
the inert protective layer comprises polydopamine and SiO 2 One or more of urea-formaldehyde resin, melamine resin, aminophenol-formaldehyde resin and polystyrene;
the perfluoropolyether chain comprises one or more of d, k, y or z type perfluoropolyether carboxylic ether, d, k, y or z type perfluoropolyether acyl chloride, d, k, y or z type perfluoropolyether acyl fluoride, d, k, y or z type perfluoropolyether amide, d, k, y or z type perfluoropolyether monoalcohol or diol, d, k, y or z type perfluoropolyether alkene perfluoropolyether allyl ether, perfluoropolyether acrylate, trimethoxy perfluoropolyether silane, triethoxy perfluoropolyether silane;
the hydrophilic group comprises one or more of polyethylene glycol, poly-N-isopropyl acrylamide, polyvinyl alcohol, N-dimethylformamide, hydroxyethyl cellulose and polyether ammonia.
2. A method for preparing a magnetic nano-functional material according to claim 1, comprising the steps of:
(1) Preparing modified magnetic nanoparticles:
dissolving magnetic nanoparticles in an organic solvent, adding dimethyl sulfoxide and dopamine hydrochloric acid, reacting for 1 to 12 hours at 50 to 100 ℃, and washing with absolute ethyl alcohol to obtain modified magnetic nanoparticles; wherein the mass ratio of the dopamine hydrochloride to the magnetic nanoparticles is 1 to 10;
(2) Coating of an inert protective layer:
adding a Tris-buffer solution into a reactor, adding the modified magnetic nanoparticles prepared in the step (1) as a substrate material and an inert protective layer material into the reactor for heating reaction, and washing with absolute ethyl alcohol to obtain magnetic nanoparticles coated by an inert protective layer; wherein the mass ratio of the base material to the inert protective layer material is 2:1, and the reaction is carried out for 1 to 10 hours under the conditions of 20 to 30 ℃;
(3) Modification of hydrophilic groups:
placing the magnetic nanoparticles coated by the inert protective layer prepared in the step (2) into a reactor, adding a Tris-buffer solution, adding a hydrophilic group, and reacting at 20 to 30 ℃ for 20 to 28 hours to obtain hydrophilic modified magnetic nanoparticles; wherein the mass ratio of the magnetic nanoparticles coated by the inert protective layer to the hydrophilic groups is 1:2;
(4) Modification of fluorocarbon chains:
placing the hydrophilic modified magnetic nanoparticles prepared in the step (3) into a reactor, adding an organic solvent, performing ultrasonic dispersion, then adding perfluoropolyether chains with different structures and an auxiliary agent, stirring, heating, reacting, washing with absolute ethyl alcohol, and drying to obtain the magnetic nano functional material; wherein the mass ratio of the base material to the perfluoropolyether chain is 1:4.
3. The method for preparing magnetic nano-functional material according to claim 2, wherein the synthesis of the strongly magnetic nanoparticles in step (1) comprises the following steps:
selecting a corresponding substrate material, adding the substrate material into a reactor, taking octyl ether as a solvent, stirring at room temperature, adding oleic acid, oleylamine and 1, 2-hexadecyl glycol, heating and stirring, continuing to heat to 100 ℃, stirring and preserving heat, then increasing the temperature to 200 ℃ at the speed of 4 ℃/min, continuing to preserve heat for a period of time, then increasing the temperature to 300 ℃ at the speed of 4 ℃/min, continuing to preserve heat for a period of time, cooling to room temperature, adding absolute ethyl alcohol and cyclohexane, washing for multiple times by using the absolute ethyl alcohol after centrifugal separation, and obtaining the ferromagnetic nanoparticles.
4. The method for preparing the magnetic nano functional material according to claim 2, wherein the product prepared in each step is stored at-10 to 10 ℃.
5. The method for preparing magnetic nano-functional material according to claim 2, characterized in that the magnetic nano-material obtained by the preparation is screened by the following steps: and (3) placing the synthesized magnetic nano material in deionized water, sealing, performing ultrasonic dispersion for 2 to 60min, placing the magnetic nano material on a neodymium magnet, standing for 2 to 60min, and cleaning particles suspended in the solution to obtain the screened magnetic nano material.
6. An application of a magnetic nano functional material in removing short-carbon-chain perfluoroalkyl compounds in a water environment is characterized in that the magnetic nano functional material is obtained by the preparation method of any one of claims 2~5, and specifically comprises the following steps:
placing the prepared magnetic nano functional material in simulated wastewater containing a short-carbon-chain perfluoroalkyl compound, dispersing for 10 to 120min by using ultrasonic, sealing, placing in a constant-temperature oscillator, and oscillating for 20 to 120min under constant temperature; and standing the mixture on a neodymium magnet for 10 to 200 seconds, taking supernatant, filtering the supernatant by using a filter membrane, and then measuring the removal rate of the short-carbon-chain perfluoroalkyl compound.
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