CN103400677A - Preparation method of magnetic Fe3O4@SiO2-NH2 nanoparticles - Google Patents

Preparation method of magnetic Fe3O4@SiO2-NH2 nanoparticles Download PDF

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CN103400677A
CN103400677A CN201310254032XA CN201310254032A CN103400677A CN 103400677 A CN103400677 A CN 103400677A CN 201310254032X A CN201310254032X A CN 201310254032XA CN 201310254032 A CN201310254032 A CN 201310254032A CN 103400677 A CN103400677 A CN 103400677A
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nano microsphere
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徐甲坤
孙谧
盛军
刘均忠
郑鸿飞
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Yellow Sea Fisheries Research Institute Chinese Academy of Fishery Sciences
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Yellow Sea Fisheries Research Institute Chinese Academy of Fishery Sciences
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Abstract

The invention relates to a preparation method of magnetic Fe3O4@SiO2-NH2 nanoparticles. The preparation method of the magnetic Fe3O4@SiO2-NH2 nanoparticles comprises the step of synthesizing of magnetic Fe3O4 nanoparticles, magnetic Fe3O4@SiO2 nanoparticles and the magnetic Fe3O4@SiO2-NH2 nanoparticles, wherein the magnetic Fe3O4 nanoparticles are spherical, even in particle size and good in dispersibility, the particle sizes of the magnetic Fe3O4 nanoparticles are 5-10 nm, and the heat stability is good. The magnetic Fe3O4@SiO2-NH2 nanoparticles are good in crystal structure, have unique magnetic property and can be used in various biotechnological fields such as magnetofluid, contrast agents, immunodetection, cell separation, biosensors, separation and purification of protein and nucleic acid, diagnostic reagents and enzyme immobilization.

Description

A kind of magnetic Fe 3O 4@SiO 2-NH 2The preparation method of Nano microsphere
Technical field
The present invention relates to field of magnetic material, particularly relate to a kind of magnetic Fe 3O 4@SiO 2-NH 2The preparation method of Nano microsphere
Background technology
Magnetic Nano material is a kind of novel magnetic material, have unique physicochemical properties, as it is little to have a particle diameter, between 1-100nm, specific area is large, and magnetic property is good, be easy to add the characteristics such as some biological function groups, therefore purposes is widely arranged in actual applications, be widely used in the biotechnology every field, as prepare the separation and purification etc. of immobilised enzymes, protein and nucleic acid.In recent years, about magnetic Nano material preparation method's research, be subject to the very large attention of scholar, wherein chemical coprecipitation has low cost, high yield and is easy to the advantages such as surface treatment.The magnetic nano-particle particle diameter that coprecipitation makes generally is positioned at 30-100nm, and the different-grain diameter of nano particle mainly is subject to cation concn, pH, the impact of ionic strength.
Magnetic Fe 3O 4Nano particle, because of its unique magnetic behavior, has unique application prospect at biomedical sector, enjoys in recent years scholar's concern.But in the situation that externally magnetic field exists, magnetic nano-particle will obtain dipole moment, and dipole moment-dipole moment interaction can cause magnetic nano-particle to form chain and cross-linked structure, thereby causes the reunion between magnetic nano-particle.In addition, naked Fe 3O 4Nano particle has very high chemism, easily oxidized in air, lose gradually magnetic and dispersiveness, therefore, it is carried out suitable surface coats or molecular modification,, to keep its stability, also can introduce various functional groups to meet specific needs in the magnetic nano particle sub-surface simultaneously.
Summary of the invention
The object of the invention is to overcome prior art and have many deficiencies, exploitation provides a kind of have unique magnetic performance and potential biotechnology applications value, can be effective to the magnetic Fe of immobilised enzymes 3O 4@SiO 2-NH 2The preparation method of Nano microsphere.
Magnetic Fe provided by the invention 3O 4@SiO 2-NH 2The preparation method of Nano microsphere, comprise the following steps:
1) magnetic Fe 3O 4Synthesizing of Nano microsphere:
Add certain water gaging (like the container size) in a container (as round-bottomed flask), the reaction system argon shield, by means of the liquid nitrogen multigelation, vacuum degassing process removes the oxygen in anhydrating, with 3.5-4.5g, preferred 4.0gFeCl 24H 2O and 9.45-12.15g, preferred 10.8gFeCl 36H 2O is in container, and argon shield, be heated to 70-90 ℃; preferred 80 ℃; after question response system homogeneous, dropwise add 29wt%37.5-62.5ml, preferred 50ml ammonia spirit becomes black; continue heating 20-30min; preferred 25min, magnetic absorption, be neutral to cleaning solution with distilled water and absolute ethyl alcohol cyclic washing respectively afterwards for several times; evaporate to dryness, obtain the black product magnetic Fe 3O 4Nano microsphere (MNP).
2) magnetic Fe 3O 4@SiO 2Synthesizing of Nano microsphere:
Magnetic Fe with step 1) 3O 4Nano microsphere 0.1-1.5g, preferred 1.0g, in the 250ml container as two mouthfuls of flasks in, add the 80ml absolute ethyl alcohol, and 20ml water, be stirred to system under ar gas environment even, ultrasonic 5-10min, preferred 10min, dropwise add ammoniacal liquor to pH8.0-11.0 under magnetic agitation, preferred 9.0, add tetraethoxysilane (TEOS) 1.0-2.5ml under ultrasonic, preferred 2.0ml, 25-60 ℃, preferred 40 ℃, reaction 2-6h, preferred 4h, magnetic absorption, for several times, evaporate to dryness obtains the product magnetic Fe for water and absolute ethanol washing product respectively 3O 4@SiO 2Nano microsphere (SMNP).
3) magnetic Fe 3O 4@SiO 2-NH 2Synthesizing of Nano microsphere:
Again with step 2) magnetic Fe 3O 4@SiO 2Nano microsphere 5-20mg; preferred 10mg in the 100ml container as two mouthfuls of flasks in, pipette 20ml toluene in two mouthfuls of flasks, argon shield; magnetic agitation is uniformly dispersed magnetic nano-particle in toluene solution; dropwise add 0.8-1.2ml, preferred 1.0ml3-aminopropyl triethoxysilane (APTES), magnetic agitation reaction 18-30h; preferred 24h; magnetic absorption, with the absolute ethanol washing product for several times, evaporate to dryness obtains the product magnetic Fe 3O 4@SiO 2-NH 2Nano microsphere (AMNP).
Magnetic Fe provided by the invention 3O 4@SiO 2-NH 2Magnetic Fe in the preparation method of Nano microsphere (or claiming nano particle) 3O 4In Nano microsphere synthetic,, take iron chloride, frerrous chloride and ammoniacal liquor as primary raw material, adopt chemical coprecipitation to prepare magnetic Fe 3O 4Nano particle, magnetic Fe 3O 4The structure of nano particle and form as seen from Figure 1, prepared magnetic Fe 3O 4The nano particle pattern is spherical, homogeneous grain diameter, and favorable dispersibility, particle diameter are 5-10nm.The Fe that this explanation makes 3O 4Nano particle is nanometer materials, magnetic Fe 3O 4Nano particle has good thermal stability.
Magnetic Fe 3O 4The infrared spectrogram of nano particle is at 579cm -1One strong absworption peak (shown in Figure 2) is arranged, herein corresponding to Fe 3O 4Middle Fe-O feature stretching vibration absworption peak, peak shape is complete,, without assorted peak, shows this magnetic Fe 3O 4Modification effect is fine.
From magnetic Fe 3O 4The XRD spectra of nano particle (shown in Figure 3) can be found out, magnetic Fe 3O 4Nano particle is 30.10 ° at 2 θ, 35.48 °, 42.89 °, 53.21 °, locates to occur diffraction maximum, the Fe of these diffraction maximums and standard for 57.19 ° and 62.88 ° 3O 4In spectrogram, (JCPDS75-1609) corresponding peak conforms to, successively corresponding to Fe 3O 4(220), (311), (400), (422), (511) and (440) crystal face.Occur assorted peak in collection of illustrative plates, show that the gained sample is the Fe of pure spinel structure 3O 4In Scherrer formula D=K λ/β cos θ formula, λ is X ray wavelength 0.15406nm, K is the peak shape factor 0.89, and D is the average grain diameter of crystal, and θ is the Bragg angle of diffraction, β is half-peak breadth, the K value depends on several factors, and its value gets 0.89, calculates the magnetic particle particle diameter, result is 7.6nm, with the ESEM result, coincide.
From magnetic Fe 3O 4The magnetic property analysis of nano particle is seen, has measured magnetic Fe under room temperature 3O 4The saturation magnetization of nano particle, result as shown in Figure 4, magnetic Fe 3O 4The remanent magnetization of nano particle and coercive force are all zero, show good superparamagnetism, and almost without hysteresis, its saturation magnetization is 47.87emu/g.
From magnetic Fe 3O 4As shown in Figure 5, result shows the thermogravimetric analysis result of nano particle, along with the rising of temperature, magnetic Fe 3O 4Nano particle is without obvious weightless peak, so, prepared magnetic Fe 3O 4Nano particle has good thermal stability.
Shown by above-mentioned characterization result: prepared magnetic Fe 3O 4Nano particle homogeneous grain diameter, favorable dispersibility, particle diameter is 7.6nm, and modification effect is better, without assorted peak, occurs, and crystal property is good.Have superparamagnetism under room temperature, saturation magnetization is 47.87emu/g, has good thermal stability.Show that the method obtains effect preferably.
The inventive method is to magnetic Fe 3O 4Nano particle has carried out surface modification, first selects tetraethoxysilane (TEOS) and magnetic Fe 3O 4The nano particle reaction, make its surface be overmolding to Fe by the silicon shell 3O 4@SiO 2, the magnetic Nano microsphere reaction of then selecting silane coupler 3-aminopropyl triethoxysilane (APTES) and silicon shell to coat, finally obtain amido modified magnetic Fe 3O 4@SiO 2-NH 2Nano microsphere, react as follows:
To magnetic Fe 3O 4In nanoparticle surface modified process, Fe 3O 4The structure of crystal does not change, and the particle phase is the Fe of inverse spinel structure 3O 4, peak shape is narrow and sharp-pointed, crystal perfection, in addition, Fe 3O 4@SiO 2, Fe 3O 4@SiO 2-NH 2The diffraction maximum of broadening has appearred in nano material near 2 θ are 20 °-25 °, intensity is little, and this is amorphous SiO 2Diffraction maximum.
Magnetic Fe 3O 4@SiO 2, Fe 3O 4@SiO 2-NH 2The tem analysis of nano particle
With TEM respectively to the preparation Fe 3O 4@SiO 2, Fe 3O 4@SiO 2-NH 2Carry out pattern and granularmetric analysis (Fig. 6-8), as seen from the figure, Fe 3O 4@SiO 2, Fe 3O 4@SiO 2-NH 2The average grain diameter of particle is about 8nm, and pattern is spherical., in conjunction with the result of the above, as seen, use TEOS, APTES to magnetic Fe 3O 4Nano particle is processed the almost not impact of size on magnetic nano-particle, thereby can guarantee that nano particle still has larger specific area after modification, keeps the high adsorption capacity of magnetic nano-particle, and reduces to modify the impact on nano particle magnetic.Magnetic Nano microsphere Fe 3O 4@SiO 2-NH 2With Fe 3O 4@NH 2Compare, can find out magnetic Fe 3O 4@SiO 2-NH 2The uniform particle diameter of Nano microsphere is better than Fe 3O 4@NH 2Nano microsphere.
Magnetic Fe 3O 4@SiO 2-NH 2Nano microsphere fourier infrared conversion spectrum figure sees Fig. 9 (corresponding respectively to a, b in figure).Magnetic Fe 3O 4@SiO 2-NH 2The preparation process of nano particle, mainly comprise Fe 3O 4@SiO 2Synthetic and Fe 3O 4@SiO 2-NH 2Preparation, can be by a in Fig. 9, and b analyzes, in a 3406 and 1632cm -1Correspond respectively to-stretching vibration and the flexural vibrations peak of OH 797 and 1081cm -1Place is respectively symmetry and the asymmetric stretching vibration absworption peak of Si-O-Si, 967cm -1And 460cm -1Place is respectively the flexural vibrations absworption peak of Si-OH and Si-O-Si, shows Fe 3O 4@SiO 2Modify successfully; 3390cm in b -1Place may for N-H stretching vibration absworption peak and-overlap peak of the stretching vibration absworption peak of OH, so can't judge amino existence, 2927cm -1Place is C-H antisymmetric stretching vibration absworption peak, 1487cm -1Place is corresponding to-CH 2The flexural vibrations absworption peak, 1330cm -1Place is corresponding to C-N key stretching vibration absworption peak, 1556cm -1Place, for N-H key deformation vibration absworption peak, shows Fe 3O 4@SiO 2-NH 2The Nanoparticle Modified success.
The XRD analysis result of magnetic nano-particle is in following table
Figure BDA00003395089200051
Can be found out Fe by Figure 10 and Biao 3O 4@SiO 2, Fe 3O 4@SiO 2-NH 2The appearance position of these diffraction maximums and the Fe of intensity and standard 3O 4Basically identical, successively corresponding to Fe 3O 4(220), (311), (400), (422), (511) and (440) crystal face.Can find out by the contrast the above results, in the process to the magnetic nano-particle finishing, Fe 3O 4The structure of crystal does not change, and the particle phase is the Fe of inverse spinel structure 3O 4, peak shape is narrow and sharp-pointed, and crystal perfection in addition, compares Fe by the XRD spectra to material 3O 4@SiO 2, Fe 3O 4@SiO 2-NH 2The diffraction maximum of broadening has appearred in nano material near 2 θ are 20 °-25 °, intensity is little, and this is amorphous SiO 2Diffraction maximum.
The magnetic property analysis of magnetic nano-particle
Fe 3O 4@SiO 2, Fe 3O 4@SiO 2-NH 2See that Deng the B-H loop of nano particle Figure 11 (correspond respectively to b in figure, c), the remanent magnetization of these 2 kinds of nano particles and coercive force are zero, all show good superparamagnetism.
Fe 3O 4@SiO 2-NH 2In the nano particle preparation process, Fe 3O 4The saturation magnetization of nano particle is 47.87emu/g, TEOS and its reaction, and after the coated Si shell, the Fe that obtains 3O 4@SiO 2The nano particle saturation magnetization is that 32.95emu/g(sees b in Figure 11), then use silane coupling A PTES and Fe 3O 4@SiO 2The nano particle reaction, after coupling amino, saturation magnetization is that 19.53emu/g(sees c in Figure 11), the Nano microsphere magnetic that obtains has certain weakening, but under the externally-applied magnetic field effect, it still can separate effectively.The thermogravimetric analysis of magnetic nano-particle
Sample F e 3O 4@SiO 2, Fe 3O 4@SiO 2-NH 2See Figure 13 (correspond respectively to a in figure, b) Deng the thermogravimetric analysis of nano particle, two kinds of nano particles are measured temperature and are all at room temperature measured.As can be known from Fig. 13, Fe 3O 4@SiO 2-NH 2In preparation process, Fe 3O 4Good thermal stability, after TEOS and its reaction, the Fe that obtains 3O 4@SiO 2Weightless approximately 13%, be mainly by SiO 2Free water in layer and in conjunction with due to the losing of water; Use silane coupling A PTES and Fe 3O 4@SiO 2After the nano particle reaction, the Fe that obtains 3O 4@SiO 2-NH 2Nano particle is weightless approximately 33.0%, is mainly by the amino content on it is modified as can be known, to be approximately 20.0%.And Fe 3O 4@NH 2In nano particle (c in figure) preparation process, weightlessness is about 2.86%, illustrates that its amino content of modifying is approximately 3%.
To magnetic Fe 3O 4Nano particle carries out surface modification, on its surface, connects amino group, obtains the amino Fe of coating 3O 4@SiO 2-NH 2Nano microsphere, by characterizing methods such as transmission electron microscope (TEM), Fourier transformation infrared spectrometer (FTIR), X-ray diffraction (XRD), superconducting quantum interference device (SQUID) (SQUID) and thermogravimetric analyzers (TGA), the Nano microsphere that makes is characterized, result shows, (1) Fe 3O 4@SiO 2-NH 2The Nano microsphere particle diameter is about 8nm, than magnetic Fe 3O 4Nano particle increases slightly, and amino group is modified successfully, and amino content is about 20%, and crystalline structure is good, has superparamagnetism, and saturation magnetization is 19.5emu/g, than raw material Fe 3O 4Nano particle obviously descends, and still, under magnetic fields, still can carry out effectively separating fast.And Fe 3O 4@NH 2The reduction of Nano microsphere uniform particle diameter, and amino content obviously reduces, and only is about 3%.
Due to Fe 3O 4@SiO 2-NH 2The relative homogeneous of Nano microsphere particle diameter, obvious many amino contents, and can realize under the externally-applied magnetic field effect effectively separating fast, therefore selection Fe 3O 4@SiO 2-NH 2Be used for the lipase immobilization research in later stage.Magnetic Fe 3O 4@SiO 2-NH 2Nano microsphere is used for lipase immobilization
Magnetic Fe with method preparation of the present invention 3O 4@SiO 2-NH 2Nano microsphere 10mg is placed in the cillin bottle container, adds the PBS buffer solution of certain volume, after infiltrating certain hour, then to adding zymoprotein concentration in container, is the lipase enzyme liquid of 0.125mg/ml, is configured to certain density enzyme liquid; Then react in shaking table, reaction temperature is 30 ℃, and pH value of reaction system is 8.0, carries out Magnetic Isolation after reaction time 10h, collect supernatant, be used for measuring protein content, after immobilised enzymes cleans for several times, until absorb without protein content in supernatant, obtain immobilised enzymes, be used for measuring immobilised enzymes.Enzymatic activity recovery can reach 87.7%, and the protein adsorption rate of unit are carrier can reach 23.7mg/g.
Magnetic Fe provided by the invention 3O 4@SiO 2-NH 2Preparation method's characteristics of Nano microsphere are
1) magnetic Fe 3O 4The nano particle pattern is spherical, homogeneous grain diameter, and favorable dispersibility, particle diameter are 5-10nm.Has good thermal stability.Crystalline structure is good, has superparamagnetism.
2) magnetic Fe 3O 4@SiO 2-NH 2The relative homogeneous of Nano microsphere particle diameter, obvious amino content how, and can realize under the externally-applied magnetic field effect effectively separating fast, have the magnetic performance of uniqueness and potential biologic applications value and combine, can be effective in immobilised enzymes.
3) be used for immobilized lipase.Enzymatic activity recovery can reach 87.7%, and the protein adsorption rate of unit are carrier can reach 23.7mg/g.
Magnetic Fe provided by the invention 3O 4@SiO 2-NH 2Nano microsphere can be applicable to the many fields of biotechnology, as separation and purification, the diagnostic reagent of magnetic fluid, contrast agent, immune detection, cell separation, biology sensor, protein and nucleic acid and can be effective to the biological fields such as enzyme immobilization.
Description of drawings
Fig. 1 Fe 3O 4The TEM photo of nano particle
Fig. 2 Fe 3O 4The fourier infrared conversion spectrum figure of nano particle
Fig. 3 magnetic Fe 3O 4The XRD spectra of nano particle
Fig. 4 magnetic Fe 3O 4The hysteresis graph of nano particle
Fig. 5 magnetic Fe 3O 4The thermogravimetric analysis of nano particle
Fig. 6-8 magnetic Fe 3O 4@SiO 2-NH 2The TEM spectrogram of nano particle
Fig. 9 magnetic Fe 3O 4@SiO 2-NH 2The fourier infrared conversion spectrum figure of nano particle
Figure 10 magnetic Fe 3O 4@SiO 2-NH 2The nano particle XRD spectra
Figure 11 magnetic Fe 3O 4@SiO 2-NH 2The B-H loop of nano particle
Figure 12 magnetic Fe 3O 4@SiO 2-NH 2The state diagram of nano particle
Figure 13 magnetic Fe 3O 4@SiO 2-NH 2The thermogravimetric analysis of nano particle
Embodiment
The present invention further illustrates the present invention with the following example, but protection scope of the present invention is not limited to the following example.
Embodiment 1
1) magnetic Fe 3O 4Synthesizing of Nano microsphere:
Add certain water gaging (like the container size) in a round-bottomed flask, the reaction system argon shield, by means of the liquid nitrogen multigelation, vacuum degassing process is except the oxygen in anhydrating, with 4.0gFeCl 24H 2O and 10.8gFeCl 36H 2O is in container; argon shield; be heated to 80 ℃; after question response system homogeneous, dropwise add the 29wt%50ml ammonia spirit to become black, continue heating 20-30min; magnetic absorption; be neutral to cleaning solution for several times with distilled water and absolute ethyl alcohol cyclic washing respectively afterwards, evaporate to dryness, obtain the black product magnetic Fe 3O 4Nano microsphere (MNP).
2) magnetic Fe 3O 4@SiO 2Synthesizing of Nano microsphere:
Magnetic Fe with step 1) 3O 4Nano microsphere 1.0g is in two mouthfuls of flasks of 250ml, add the 80ml absolute ethyl alcohol, and 20ml water, 10min stirred under ar gas environment even to system, ultrasonic 10min, dropwise add ammoniacal liquor 1.6ml to pH9.0 under magnetic agitation, add tetraethoxysilane (TEOS) 2.0ml under ultrasonic, 40 ℃ of reaction 4h, magnetic absorption, for several times, evaporate to dryness, obtain the product magnetic Fe for water and absolute ethanol washing product respectively 3O 4@SiO 2Nano microsphere (SMNP).
3) magnetic Fe 3O 4@SiO 2-NH 2Synthesizing of Nano microsphere (AMNP):
Again with step 2) magnetic Fe 3O 4@SiO 2Nano microsphere 10mg is in two mouthfuls of flasks of 100ml; pipette 20ml toluene in two mouthfuls of flasks; argon shield; magnetic agitation is disperseed magnetic nano-particle in toluene solution; dropwise add the 1.0ml3-aminopropyl triethoxysilane, magnetic agitation reaction 24h, magnetic absorption; with the absolute ethanol washing product for several times, evaporate to dryness obtains the product magnetic Fe 3O 4@SiO 2-NH 2Nano microsphere (AMNP).
Embodiment 2
1) magnetic Fe 3O 4Synthesizing of Nano microsphere:
Add certain water gaging (like the container size) in a round-bottomed flask, the reaction system argon shield, by means of the liquid nitrogen multigelation, vacuum degassing process is except the oxygen in anhydrating, with 3.5gFeCl 24H 2O and 9.45gFeCl 36H 2O is in container; argon shield; be heated to 70 ℃; after question response system homogeneous, dropwise add the 29wt%37.5ml ammonia spirit to become black, continue heating 20min; magnetic absorption; be neutral to cleaning solution for several times with distilled water and absolute ethyl alcohol cyclic washing respectively afterwards, evaporate to dryness, obtain the black product magnetic Fe 3O 4Nano microsphere (MNP).
2) magnetic Fe 3O 4@SiO 2Synthesizing of Nano microsphere:
Magnetic Fe with step 1) 3O 4Nano microsphere 0.1g is in two mouthfuls of flasks of 250ml, add the 80ml absolute ethyl alcohol, and 20ml water, stir 10min under ar gas environment even to system, ultrasonic 5min, dropwise add ammoniacal liquor under magnetic agitation to pH8.0, add tetraethoxysilane (TEOS) 1.0ml under ultrasonic, 25 ℃ of reaction 2h, magnetic absorption, for several times, evaporate to dryness obtains the product magnetic Fe for water and absolute ethanol washing product respectively 3O 4@SiO 2Nano microsphere (SMNP).
3) magnetic Fe 3O 4@SiO 2-NH 2Synthesizing of Nano microsphere (AMNP):
Again with step 2) magnetic Fe 3O 4@SiO 2Nano microsphere 5mg is in two mouthfuls of flasks of 100ml; pipette 20ml toluene in two mouthfuls of flasks; argon shield; magnetic agitation is disperseed magnetic nano-particle in toluene solution; dropwise add the 0.8ml3-aminopropyl triethoxysilane, magnetic agitation reaction 18h, magnetic absorption; with the absolute ethanol washing product for several times, evaporate to dryness obtains the product magnetic Fe 3O 4@SiO 2-NH 2Nano microsphere (AMNP).
Embodiment 3
1), add certain water gaging (like container size) in round-bottomed flask, the reaction system argon shield, by means of the liquid nitrogen multigelation, vacuum degassing process is except the oxygen in anhydrating, with 4.5gFeCl 24H 2O and 12.15gFeCl 36H 2O is in container; argon shield; be heated to 90 ℃; after question response system homogeneous, dropwise add the 29wt%62.5ml ammonia spirit to become black, continue heating 20-30min; magnetic absorption; be neutral to cleaning solution for several times with distilled water and absolute ethyl alcohol cyclic washing respectively afterwards, evaporate to dryness, obtain the black product magnetic Fe 3O 4Nano microsphere (MNP).
2) magnetic Fe 3O 4@SiO 2Synthesizing of Nano microsphere:
Magnetic Fe with step 1) 3O 4Nano microsphere 1.5g is in two mouthfuls of flasks of 250ml, add the 80ml absolute ethyl alcohol, and 20ml water, stir 10min under ar gas environment even to system, ultrasonic 10min, dropwise add ammoniacal liquor under magnetic agitation to pH11.0, add tetraethoxysilane (TEOS) 2.5ml under ultrasonic, 60 ℃ of reaction 6h, magnetic absorption, for several times, evaporate to dryness obtains the product magnetic Fe for water and absolute ethanol washing product respectively 3O 4@SiO 2Nano microsphere (SMNP).
3) magnetic Fe 3O 4@SiO 2-NH 2Synthesizing of Nano microsphere (AMNP):
Again with step 2) magnetic Fe 3O 4@SiO 2Nano microsphere 20mg is in two mouthfuls of flasks of 100ml; pipette 20ml toluene in two mouthfuls of flasks; argon shield; magnetic agitation is disperseed magnetic nano-particle in toluene solution; dropwise add the 1.2ml3-aminopropyl triethoxysilane, magnetic agitation reaction 30h, magnetic absorption; with the absolute ethanol washing product for several times, evaporate to dryness obtains the product magnetic Fe 3O 4@SiO 2-NH 2Nano microsphere (AMNP).

Claims (2)

1. magnetic Fe 3O 4@SiO 2-NH 2The preparation method of Nano microsphere, comprise the following steps:
1) magnetic Fe 3O 4Synthesizing of Nano microsphere:
Add certain water gaging in a container, the reaction system argon shield, by means of the liquid nitrogen multigelation, vacuum degassing process is except the oxygen in anhydrating, with 3.5-4.5gFeCl 24H 2O and 9.45-12.15gFeCl 36H 2O is in container; argon shield; be heated to 70-90 ℃; after question response system homogeneous, dropwise add the 29wt%37.5-62.5ml ammonia spirit to become black, continue heating 20-30min; magnetic absorption; be neutral to cleaning solution for several times with distilled water and absolute ethyl alcohol cyclic washing respectively afterwards, evaporate to dryness, obtain the black product magnetic Fe 3O 4Nano microsphere;
2) magnetic Fe 3O 4@SiO 2Synthesizing of Nano microsphere:
Magnetic Fe with step 1) 3O 4Nano microsphere 0.1-1.5g is in the 250ml container, add the 80ml absolute ethyl alcohol, and 20ml water, be stirred to system under ar gas environment even, ultrasonic 5-10min, dropwise add ammoniacal liquor under magnetic agitation to pH8.0-11.0, add tetraethoxysilane 1.0-2.5ml under ultrasonic, 25-60 ℃ of reaction 2-6h, magnetic absorption, for several times, evaporate to dryness obtains the product magnetic Fe for water and absolute ethanol washing product respectively 3O 4@SiO 2Nano microsphere;
3) magnetic Fe 3O 4@SiO 2-NH 2Synthesizing of Nano microsphere:
Again with step 2) magnetic Fe 3O 4@SiO2 Nano microsphere 5-20mg is in the 100ml container; pipette 20ml toluene in container; argon shield; magnetic agitation is disperseed magnetic nano-particle in toluene solution; dropwise add the 0.8-1.2ml3-aminopropyl triethoxysilane, magnetic agitation reaction 18-30h, magnetic absorption; with the absolute ethanol washing product for several times, evaporate to dryness obtains the product magnetic Fe 3O 4@SiO 2-NH 2Nano microsphere.
2. magnetic Fe 3O 4@SiO 2-NH 2Nano microsphere, is characterized in that the magnetic Fe by claim 1 3O 4@SiO 2-NH 2The magnetic Fe of preparation method's preparation of Nano microsphere 3O 4@SiO 2-NH 2Nano microsphere.
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CN110317583A (en) * 2018-03-29 2019-10-11 中国石油化工股份有限公司 Magnetic intelligence controllable foam system and preparation method thereof
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CN111063500A (en) * 2020-01-10 2020-04-24 中山大学 Modified magnetic nano-particles, non-polar solvent-based magnetic liquid, preparation method and application

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