CN107999019B - Amphiphilic magnetic nanosphere and preparation method and adsorption application thereof - Google Patents

Amphiphilic magnetic nanosphere and preparation method and adsorption application thereof Download PDF

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CN107999019B
CN107999019B CN201711240531.8A CN201711240531A CN107999019B CN 107999019 B CN107999019 B CN 107999019B CN 201711240531 A CN201711240531 A CN 201711240531A CN 107999019 B CN107999019 B CN 107999019B
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高瑞霞
高路瑶
唐骁爽
张军杰
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Xian Jiaotong University
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Abstract

The invention discloses an amphiphilic magnetic nanosphere and a preparation method and an adsorption application thereof, and belongs to the technical field of nano material preparation and environment detection. Firstly, magnetic Fe is synthesized by a solvothermal method3O4Nanospheres; then, under the alkaline condition, a silanization reagent 3-aminopropyl triethoxysilane containing amino and a silanization reagent n-octyl triethoxysilane containing long-chain alkyl are grafted on the surface of the carrier through the sol-gel effect, and the amphiphilic modification of the magnetic nanospheres is realized in one step. The preparation method is simple and mild in condition, and the prepared amphiphilic magnetic nanospheres are uniform in particle size, strong in stability, good in hydrophilicity, large in dioctyl phthalate adsorption capacity and high in adsorption speed, and can be used for conveniently, efficiently and quickly removing and enriching dioctyl phthalate in an environmental water sample.

Description

Amphiphilic magnetic nanosphere and preparation method and adsorption application thereof
Technical Field
The invention belongs to the technical field of nano material preparation and environment detection, and particularly relates to an amphiphilic magnetic nanosphere and a preparation method and an adsorption application thereof.
Background
Phthalates (PAEs), or plasticizers, have been widely used in a variety of industrial products, primarily as polymer additives to improve the moldability of packaging articles such as plastics, medical devices, toys for children, and food. Some studies have shown that the effects of PAEs are similar to the effects of estrogens. Even at very low concentrations, PAEs may cause gynogenesis and disorders of reproductive development and maturation, affecting the balance of normal hormonal functions in animals and humans. Laboratory testing in rodents has shown that high exposure of PAEs can damage the liver, kidneys and lungs. In addition, PAEs can easily leach out of plastic packaging and into the environment. PAEs have been given priority by the U.S. environmental protection agency as a pollutant.
Dioctyl phthalate (DOP) is an important general-purpose plasticizer in the PAEs family. DOP is a hydrophobic environmentally hazardous substance, and its release and adsorption are mostly carried out in an aqueous environment by hydrophobic interactions. Some DOP adsorption materials reported previously are DOP molecularly imprinted polymers prepared by a molecular imprinting technology, and although the adsorption materials have certain adsorption capacity for DOP, the adsorption experiment operation process is complicated and long in time consumption, after the materials are synthesized, a quite long time is needed for elution of template molecules, and in the elution process, a large amount of solvents are consumed by repeatedly replacing and detecting the solvents, so that the green chemistry principle is violated, and great defects exist; some adsorbing materials lack magnetic responsiveness, and a complex centrifugal separation process is required in the experimental process, so that the experimental period is not shortened; some adsorbing materials lack good hydrophilic characteristics, are poor in dispersibility in an environmental water sample, increase in adsorption energy barrier, and prevent the adsorbing materials from being uniformly dispersed in water, and are not suitable for being used in a water environment. Therefore, the development of a simple and effective method for preparing the amphiphilic magnetic adsorption nano material has important research significance for realizing efficient enrichment, effective detection, rapid removal and the like of DOP in an environmental water sample.
A sol-gel method for preparing nano particles and needed material features that inorganic substance or metal alkoxide is used as precursor, the raw material is dispersed in solvent, the hydrolytic reaction is performed to generate active monomer, the active monomer is polymerized to become sol, and the gel with a certain space structure is dried and thermally treated to obtain nano particles and needed material. The sol-gel process combines organic functional groups with inorganic precursors, can introduce specific chemical functional groups into a network structure of a polymer, is easy to prepare a porous polymer with high crosslinking degree and good thermal stability and chemical stability, and provides an efficient method for preparing an organic-inorganic hybrid material with excellent performance.
In the traditional solid phase extraction, an adsorbent is generally in a powder shape, and although the adsorbent has good adsorption performance, the solid-liquid separation is difficult. The magnetic solid phase extraction technology is used as a new mode of solid phase extraction, and shows wide application prospect in the field of separation science. Magnetic separation is one of the effective means for recovering and utilizing powder, and the processed magnetic material can be used as an adsorbent for solid phase extraction, so that the separation can be simply and efficiently carried out. In magnetic separation, the adsorbent does not need to be filled into an adsorption column, complex steps such as centrifugation, filtration and the like are not needed, and the phase separation can be realized only by one external magnetic field. The operation process of the magnetic solid phase extraction is simple and quick, and the interface area between the adsorbent and the sample solution is greatly increased through dispersion or suspension extraction, so that the mass transfer rate is improved, and the separation of trace substances in a large-volume sample can be realized in a short time; compared with the traditional extraction method, the magnetic solid phase extraction has obvious advantages in the aspects of reagent dosage, extraction efficiency, operation process and the like.
At present, no relevant report about the technology of separating and enriching DOP in environmental water samples by using the amphiphilic magnetic adsorption material is found.
Disclosure of Invention
The invention aims to provide an amphiphilic magnetic nanosphere and a preparation method and an adsorption application thereof, the method is simple to operate and mild in condition, and surface grafting and hydrophilic-hydrophobic modification of a carrier are realized simultaneously by a sol-gel method under an alkaline condition; the amphiphilic magnetic nanospheres prepared by the method have the advantages of uniform particle size, strong stability, good hydrophilicity, strong DOP adsorption capacity in an aqueous solution and large adsorption quantity.
The invention is realized by the following technical scheme:
the invention discloses a preparation method of an amphiphilic magnetic nanosphere, which comprises the following steps: firstly, the magnetic Fe is synthesized by solvothermal method3O4Nanospheres; then magnetic Fe3O4The nanospheres are used as carriers, and under the alkaline condition, a silanization reagent containing amino and a silanization reagent containing long-chain alkyl are grafted on the surfaces of the carriers through the sol-gel effect to realize the amphiphilic modification of the magnetic nanospheres so as to prepare the amphiphilic magnetic nanospheres;
wherein the silylation agent containing amino is 3-aminopropyltriethoxysilane, and the silylation agent containing long chain alkyl is n-octyltriethoxysilane.
Preferably, the preparation method of the amphiphilic magnetic nanosphere comprises the following steps:
the method comprises the following steps: a g ferric trichloride and B g anhydrous sodium acetate are dissolved in a reaction kettle containing C mL ethylene glycol, the mixture is uniformly stirred, the reaction kettle is kept at 180-210 ℃ for 7-9 hours, after the reaction is finished, the reaction kettle is naturally cooled to room temperature, and a reaction product is washed and dried in vacuum to obtain magnetic Fe3O4Nanospheres;
wherein, A, B, C, A, B, C;
step two: d g magnetic Fe3O4Adding the nanospheres into E mL of water-ethanol solution, performing ultrasonic oscillation until the nanospheres are uniformly dispersed, then respectively adding F mL of 3-aminopropyltriethoxysilane and G mL of n-octyltriethoxysilane, and mechanically stirring for 1-3 hours at room temperature; then adding H mL ammonia water, and reacting at room temperature for 20-60 min;
wherein, D and E are F, G, H, (0.1-0.3), (70-90), (0.5-2.5) and (4.0-5.0).
Step three: and after the sol-gel polymerization reaction in the second step is finished, separating out the solid polymer generated in the reaction liquid through an external magnetic field, washing and drying to obtain the amphiphilic magnetic nanospheres.
Preferably, in the first step, the reaction product is washed to be neutral by ultrapure water, and then dried for 4-7 hours in vacuum at 40-50 ℃ and 0.05-0.09 MPa.
Preferably, the water-ethanol solution is prepared by mixing water and absolute ethanol in a volume ratio of (8-10): 1; the ammonia water used is 24% by mass.
Preferably, the stirring speed of the mechanical stirring at room temperature is 200-500 r/min.
Preferably, the volume ratio of 3-aminopropyltriethoxysilane to n-octyltriethoxysilane is 1: 1.
Preferably, the washing is carried out by washing the separated solid polymer with ultrapure water; the drying temperature is 40-50 ℃, and the drying time is 4-7 h.
The invention also discloses the amphiphilic magnetic nanosphere prepared by the preparation method, and the amphiphilic magnetic nanosphere can adsorb dioctyl phthalate, and the adsorption quantity is 250-273 mg/g.
The invention also discloses application of the amphiphilic magnetic nanosphere as a dioctyl phthalate adsorbent.
The invention also discloses application of the amphiphilic magnetic nanosphere in adsorption of dioctyl phthalate in an environmental water sample.
Compared with the prior art, the invention has the following beneficial technical effects:
the preparation method of the amphipathic magnetic nanosphere provided by the invention comprises the following steps of firstly, synthesizing magnetic Fe by a solvothermal method3O4Nanospheres; then, with magnetic Fe3O4The nanospheres are used as carriers, and under the alkaline condition, a silanization reagent 3-aminopropyl triethoxysilane containing amino and a silanization reagent n-octyl triethoxysilane containing long-chain alkyl are grafted on the surfaces of the carriers through the sol-gel effect, so that the amphiphilic modification of the magnetic nanospheres is realized. The amino group grafted on the surface of the carrier has better hydrophilicity, and can improve the dispersibility of the adsorbent in water; the grafted alkyl chain has stronger hydrophobicity, and can adsorb DOP in an environmental water sample through the hydrophobic effect; and finally, separating the solid polymer by an external magnetic field, washing with ultrapure water, and drying to obtain the amphiphilic magnetic nanospheres. Compared with the synthesis method of other types of adsorbents, the preparation method is simple and mild in condition, and surface grafting and hydrophilic and hydrophobic modification of the carrier are simultaneously realized by a sol-gel method under an alkaline condition. Not only ensures the good dispersibility of the adsorbing material in the water solution, but also promotes the full action of the adsorbing material and the hydrophobic DOP.
The amphiphilic magnetic nanospheres prepared by the method have the advantages of uniform particle size, strong stability, good hydrophilicity, strong DOP adsorption capacity in an aqueous solution, large adsorption quantity, capability of simply, conveniently, efficiently and quickly removing, separating and enriching DOP in an environmental water sample, and good application prospect in the aspects of enrichment, detection, separation, removal and the like of PAEs in the environmental water sample.
Drawings
FIG. 1 shows magnetic Fe synthesized in step one of example 1 of the present invention3O4Transmission electron microscopy of nanospheres.
Fig. 2 is a transmission electron microscope image of the amphiphilic magnetic nanospheres prepared 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.
Example 1
A preparation method of the amphiphilic magnetic nanosphere comprises the following steps:
step one, 1.38g of ferric trichloride and 3.7g of anhydrous sodium acetate are dissolved in a 50mL Teflon-lined stainless steel high-pressure reaction kettle containing 39mL of ethylene glycol, and after uniform stirring, the reaction kettle is kept at 203 ℃ for 8.5 h. After the reaction is finished, naturally cooling to room temperature, washing the reaction product to be neutral by using ultrapure water, and drying for 4.5 hours in vacuum at 45 ℃ under 0.06MPa to obtain the magnetic Fe3O4Nanoparticles. Magnetic Fe produced as shown in FIG. 13O4The particle size of the nanospheres is about 200 nm.
Step two, weighing 0.2g of magnetic Fe prepared in the step one3O4Nanoparticles, 80mL of water-ethanol solution, were placed in a 250mL three-necked flask and dispersed uniformly by ultrasonic oscillation. To this was added 3-aminopropyltriethoxysilane and 1.5mL n-octyltriethoxysilane, respectively, and the mixture was mechanically stirred at 260r/min for 2h at room temperature. Then, 4.8mL of ammonia was added thereto and the reaction was carried out at room temperature for 30 min.
Step three, after the sol-gel polymerization reaction in the step two is finished, separating out the solid polymer generated in the reaction liquid through an external magnetic field; and washing the separated solid polymer by ultrapure water, and drying at 40 ℃ for 4h to obtain the amphiphilic magnetic nanospheres. As shown in fig. 2, the prepared amphiphilic magnetic nanosphere has a particle size of about 210 nm.
The amphiphilic magnetic nanospheres prepared in example 1 were tested for adsorption performance as follows:
(1) adding 10mg of the amphiphilic magnetic nanospheres into 10mL of DOP aqueous solution with the concentration of 400 mug/mL, oscillating for 2min at room temperature, and separating out supernate through an external magnetic field; then 10mL of ethanol is added into the beaker containing the residual solid, the mixture is shaken for 1min at room temperature for desorption, and the solution after desorption is separated out by an external magnetic field.
(2) Measuring the DOP concentration in the desorption solution obtained in the step (1) by using a gas chromatograph, and then calculating the DOP adsorption amount of the amphiphilic magnetic nanospheres;
the measured DOP concentration in the desorption solution was 273. mu.g/mL;
the calculation formula of the DOP adsorption amount of the amphiphilic magnetic nanospheres is as follows:
Figure BDA0001489721630000061
in the formula CAnalysis ofThe concentration of DOP in the desorption solution;
by calculation, the adsorption amount of the amphiphilic magnetic nanosphere to DOP is as follows: 273 mg/g.
Example 2
A preparation method of the amphiphilic magnetic nanosphere comprises the following steps:
step one, 1.25g of ferric trichloride and 3.4g of anhydrous sodium acetate are dissolved in a 50mL Teflon-lined stainless steel high-pressure reaction kettle containing 20mL of ethylene glycol, and after the mixture is uniformly stirred, the reaction kettle is kept at 180 ℃ for 7 hours. After the reaction is finished, naturally cooling to room temperature, washing the reaction product to be neutral by using ultrapure water, and drying for 4 hours in vacuum at 40 ℃ and under 0.05MPa to obtain the magnetic Fe3O4Nanoparticles.
Step two, weighing 0.10g of magnetic Fe prepared in the step one3O4Nanoparticles, 70mL of water-ethanol solution, were placed in a 250mL three-necked flask and dispersed uniformly by ultrasonic oscillation. 0.5mL 3-aminopropyltriethoxysilane and 0.5mL n-octyltriethoxysilane were added to each flask and mechanically stirred at 200r/min for 1h at room temperature. Then, 4.0mL of ammonia was added thereto and the reaction was carried out at room temperature for 20 min.
Step three, after the sol-gel polymerization reaction in the step two is finished, separating out the solid polymer generated in the reaction liquid through an external magnetic field; and washing the separated solid polymer by ultrapure water, and drying at 40 ℃ for 4h to obtain the amphiphilic magnetic nanospheres.
The amphiphilic magnetic nanospheres prepared in example 2 were tested for adsorption performance as follows:
(1) adding 10mg of the amphiphilic magnetic nanospheres into 10mL of DOP aqueous solution with the concentration of 400 mug/mL, oscillating for 2min at room temperature, and separating out supernate through an external magnetic field; then 10mL of ethanol is added into the beaker containing the residual solid, the mixture is shaken for 1min at room temperature for desorption, and the solution after desorption is separated out by an external magnetic field.
(2) Measuring the DOP concentration in the desorption solution obtained in the step (1) by using a gas chromatograph, and then calculating the DOP adsorption amount of the amphiphilic magnetic nanospheres;
the measured DOP concentration in the desorption solution was 256. mu.g/mL;
the calculation formula of the DOP adsorption amount of the amphiphilic magnetic nanospheres is as follows:
Figure BDA0001489721630000071
in the formula CAnalysis ofThe concentration of DOP in the desorption solution;
by calculation, the adsorption amount of the amphiphilic magnetic nanosphere to DOP is as follows: 256 mg/g.
Example 3
A preparation method of the amphiphilic magnetic nanosphere comprises the following steps:
step one, 1.45g of ferric trichloride and 3.8g of anhydrous sodium acetate are dissolved in a 50mL Teflon-lined stainless steel high-pressure reaction kettle containing 35mL of ethylene glycol, and after the mixture is uniformly stirred, the reaction kettle is kept at 210 ℃ for 9 hours. After the reaction is finished, naturally cooling to room temperature, washing the reaction product to be neutral by using ultrapure water, and drying for 7 hours in vacuum at 50 ℃ and 0.09MPa to obtain the magnetic Fe3O4Nanoparticles.
Step two, weighing 0.30g of the magnetic Fe prepared in the step one3O4The nano particles and 90mL of water-ethanol solution are placed in a 250mL three-neck flask and are uniformly dispersed by ultrasonic oscillation. 2.5mL 3-aminopropyltriethoxysilane and 2.5mL n-octyltriethoxysilane were added, respectively, and mechanically stirred at 500r/min for 3h at room temperature. Then, 5.0mL of ammonia water was added thereto and the reaction was carried out at room temperature for 60 min.
Step three, after the sol-gel polymerization reaction in the step two is finished, separating out the solid polymer generated in the reaction liquid through an external magnetic field; and washing the separated solid polymer by ultrapure water, and drying at 50 ℃ for 7h to obtain the amphiphilic magnetic nanospheres.
The amphiphilic magnetic nanospheres prepared in example 3 were tested for adsorption performance as follows:
(1) adding 10mg of the amphiphilic magnetic nanospheres into 10mL of DOP aqueous solution with the concentration of 400 mug/mL, oscillating for 2min at room temperature, and separating out supernate through an external magnetic field; then 10mL of ethanol is added into the beaker containing the residual solid, the mixture is shaken for 1min at room temperature for desorption, and the solution after desorption is separated out by an external magnetic field.
(2) Measuring the DOP concentration in the desorption solution obtained in the step (1) by using a gas chromatograph, and then calculating the DOP adsorption amount of the amphiphilic magnetic nanospheres;
the measured DOP concentration in the desorption solution was 269. mu.g/mL;
the calculation formula of the DOP adsorption amount of the amphiphilic magnetic nanospheres is as follows:
Figure BDA0001489721630000081
in the formula CAnalysis ofThe concentration of DOP in the desorption solution;
by calculation, the adsorption amount of the amphiphilic magnetic nanosphere to DOP is as follows: 269 mg/g.
Example 4
A preparation method of the amphiphilic magnetic nanosphere comprises the following steps:
step (ii) ofFirstly, 1.30g of ferric trichloride and 3.7g of anhydrous sodium acetate are dissolved in a 50mL Teflon-lined stainless steel high-pressure reaction kettle containing 25mL of ethylene glycol, and after uniform stirring, the reaction kettle is kept at 195 ℃ for 8.5 h. After the reaction is finished, naturally cooling to room temperature, washing the reaction product to be neutral by using ultrapure water, and drying for 7 hours in vacuum at 47 ℃ under 0.09MPa to obtain the magnetic Fe3O4Nanoparticles.
Step two, weighing 0.28g of magnetic Fe prepared in the step one3O4Nanoparticles, 80mL of water-ethanol solution, were placed in a 250mL three-necked flask and dispersed uniformly by ultrasonic oscillation. 2.0mL 3-aminopropyltriethoxysilane and 2.0mL n-octyltriethoxysilane were added, respectively, and mechanically stirred at 400r/min for 1.5h at room temperature. Then, 4.0mL of ammonia was added thereto and the reaction was carried out at room temperature for 50 min.
Step three, after the sol-gel polymerization reaction in the step two is finished, separating out the solid polymer generated in the reaction liquid through an external magnetic field; and washing the separated solid polymer by ultrapure water, and drying at 45 ℃ for 7h to obtain the amphiphilic magnetic nanospheres.
The amphiphilic magnetic nanospheres prepared in example 4 were tested for adsorption performance as follows:
(1) adding 10mg of the amphiphilic magnetic nanospheres into 10mL of DOP aqueous solution with the concentration of 400 mug/mL, oscillating for 2min at room temperature, and separating out supernate through an external magnetic field; then 10mL of ethanol is added into the beaker containing the residual solid, the mixture is shaken for 1min at room temperature for desorption, and the solution after desorption is separated out by an external magnetic field.
(2) Measuring the DOP concentration in the desorption solution obtained in the step (1) by using a gas chromatograph, and then calculating the DOP adsorption amount of the amphiphilic magnetic nanospheres;
the measured concentration of DOP in the desorption solution was 250. mu.g/mL;
the calculation formula of the DOP adsorption amount of the amphiphilic magnetic nanospheres is as follows:
Figure BDA0001489721630000091
in the formula CAnalysis ofThe concentration of DOP in the desorption solution;
by calculation, the adsorption amount of the amphiphilic magnetic nanosphere to DOP is as follows: 250 mg/g.
Example 5
A preparation method of the amphiphilic magnetic nanosphere comprises the following steps:
step one, 1.28g of ferric trichloride and 3.5g of anhydrous sodium acetate are dissolved in a 50mL Teflon-lined stainless steel high-pressure reaction kettle containing 20mL of ethylene glycol, and after uniform stirring, the reaction kettle is kept at 180 ℃ for 7.5 h. After the reaction is finished, naturally cooling to room temperature, washing the reaction product to be neutral by using ultrapure water, and drying for 5 hours in vacuum at 44 ℃ and 0.08MPa to obtain the magnetic Fe3O4Nanoparticles.
Step two, weighing 0.18g of magnetic Fe prepared in the step one3O4The nano particles, 85mL water-ethanol solution are put in a 250mL three-neck flask and are dispersed evenly by ultrasonic oscillation. To this was added 3-aminopropyltriethoxysilane and 1.9mL n-octyltriethoxysilane, respectively, and the mixture was mechanically stirred at 460r/min for 1.5h at room temperature. Then, 4.2mL of ammonia was added and the reaction was carried out at room temperature for 20 min.
Step three, after the sol-gel polymerization reaction in the step two is finished, separating out the solid polymer generated in the reaction liquid through an external magnetic field; and washing the separated solid polymer by ultrapure water, and drying at 46 ℃ for 6.5 hours to obtain the amphiphilic magnetic nanospheres.
The amphiphilic magnetic nanospheres prepared in example 5 were tested for adsorption performance as follows:
(1) adding 10mg of the amphiphilic magnetic nanospheres into 10mL of DOP aqueous solution with the concentration of 400 mug/mL, oscillating for 2min at room temperature, and separating out supernate through an external magnetic field; then 10mL of ethanol is added into the beaker containing the residual solid, the mixture is shaken for 1min at room temperature for desorption, and the solution after desorption is separated out by an external magnetic field.
(2) Measuring the DOP concentration in the desorption solution obtained in the step (1) by using a gas chromatograph, and then calculating the DOP adsorption amount of the amphiphilic magnetic nanospheres;
the measured concentration of DOP in the desorption solution was 271. mu.g/mL;
the calculation formula of the DOP adsorption amount of the amphiphilic magnetic nanospheres is as follows:
Figure BDA0001489721630000101
in the formula CAnalysis ofThe concentration of DOP in the desorption solution;
by calculation, the adsorption amount of the amphiphilic magnetic nanosphere to DOP is as follows: 271 mg/g.
Example 6
A preparation method of the amphiphilic magnetic nanosphere comprises the following steps:
step one, dissolving 1.40g of ferric trichloride and 3.65g of anhydrous sodium acetate in a 50mL high-pressure reaction kettle containing 22mL of ethylene glycol, stirring uniformly, and keeping the reaction kettle at 205 ℃ for 7.2 h. After the reaction is finished, naturally cooling to room temperature, washing the reaction product to be neutral by using ultrapure water, and drying for 6.5h in vacuum at the temperature of 46 ℃ and under the pressure of 0.09MPa to obtain the magnetic Fe3O4Nanoparticles.
Step two, weighing 0.1g of magnetic Fe prepared in the step one3O4Nanoparticles, 70mL of water-ethanol solution, were placed in a 250mL three-necked flask and dispersed uniformly by ultrasonic oscillation. To this was added 3-aminopropyltriethoxysilane and 1.0mL n-octyltriethoxysilane, respectively, and mechanically stirred at room temperature for 1 h. Then, 5.0mL of ammonia water was added thereto and reacted at room temperature for 45 min.
Step three, after the sol-gel polymerization reaction in the step two is finished, separating out the solid polymer generated in the reaction liquid through an external magnetic field; and washing the separated solid polymer by ultrapure water, and drying at 47 ℃ for 5 hours to obtain the amphiphilic magnetic nanospheres.
The amphiphilic magnetic nanospheres prepared in example 6 were tested for adsorption performance as follows:
(1) adding 10mg of the amphiphilic magnetic nanospheres into 10mL of DOP aqueous solution with the concentration of 400 mug/mL, oscillating for 2min at room temperature, and separating out supernate through an external magnetic field; then 10mL of ethanol is added into the beaker containing the residual solid, the mixture is shaken for 1min at room temperature for desorption, and the solution after desorption is separated out by an external magnetic field.
(2) Measuring the DOP concentration in the desorption solution obtained in the step (1) by using a gas chromatograph, and then calculating the DOP adsorption amount of the amphiphilic magnetic nanospheres;
the measured DOP concentration in the desorption solution was 263. mu.g/mL;
the calculation formula of the DOP adsorption amount of the amphiphilic magnetic nanospheres is as follows:
Figure BDA0001489721630000111
in the formula CAnalysis ofThe concentration of DOP in the desorption solution;
by calculation, the adsorption amount of the amphiphilic magnetic nanosphere to DOP is as follows: 263 mg/g.
The above description is only a preferred embodiment of the present invention, and is not intended to limit the present invention, and all simple modifications, changes and equivalent structural changes made to the above embodiment according to the technical spirit of the present invention still fall within the protection scope of the technical solution of the present invention.

Claims (7)

1. The application of the amphiphilic magnetic nanospheres as dioctyl phthalate adsorbents is characterized in that the amphiphilic magnetic nanospheres can adsorb dioctyl phthalate, and the adsorption capacity is 250-273 mg/g;
the preparation method of the amphiphilic magnetic nanosphere comprises the following steps:
the method comprises the following steps: a g ferric trichloride and B g anhydrous sodium acetate are dissolved in a reaction kettle containing C mL ethylene glycol, and after the mixture is uniformly stirred, the reaction kettle is stirred for 180-210 hoursoKeeping the temperature for 7-9 h under C, naturally cooling to room temperature after the reaction is finished, washing and vacuum drying the reaction product to obtain the magnetic Fe3O4Nanospheres;
wherein A is B, C = (1.25-1.45), (3.4-3.8) and (20-35);
step two: d g magnetic Fe3O4Adding the nanospheres into E mL of water-ethanol solution, performing ultrasonic oscillation until the nanospheres are uniformly dispersed, then respectively adding F mL of 3-aminopropyltriethoxysilane and G mL of n-octyltriethoxysilane, and mechanically stirring for 1-3 hours at room temperature; then adding H mL ammonia water, and reacting at room temperature for 20-60 min;
wherein, D, E, F, G, H = (0.1-0.3), 70-90, (0.5-2.5), 0.5-2.5, and (4.0-5.0);
step three: and after the sol-gel polymerization reaction in the second step is finished, separating out the solid polymer generated in the reaction liquid through an external magnetic field, washing and drying to obtain the amphiphilic magnetic nanospheres.
2. The use of claim 1, wherein in the first step, the reaction product is washed to neutral with ultrapure water, and then dried under vacuum at 40-50 ℃ and 0.05-0.09 MPa for 4-7 h.
3. The application of the composition as claimed in claim 1, wherein in the second step, the water-ethanol solution is prepared by mixing water and absolute ethanol in a volume ratio of (8-10): 1; the ammonia water used is 24% by mass.
4. The use according to claim 1, wherein in the second step, the stirring rate of the mechanical stirring at room temperature is 200 to 500 r/min.
5. The use of claim 1, wherein in step two, the volume ratio of 3-aminopropyltriethoxysilane to n-octyltriethoxysilane is 1: 1.
6. The use according to claim 1, wherein in step three, the washing is carried out by washing the separated solid polymer with ultrapure water; the drying temperature is 40-50 ℃, and the drying time is 4-7 h.
7. The use of claim 1, wherein said amphiphilic magnetic nanospheres are capable of adsorbing dioctyl phthalate in an environmental water sample.
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