CN106693920A - Magnetic nano composite material and a preparation method and application thereof - Google Patents

Magnetic nano composite material and a preparation method and application thereof Download PDF

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CN106693920A
CN106693920A CN201710079429.8A CN201710079429A CN106693920A CN 106693920 A CN106693920 A CN 106693920A CN 201710079429 A CN201710079429 A CN 201710079429A CN 106693920 A CN106693920 A CN 106693920A
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teta
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王帆
张丽娟
陆杰
樊学学
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Shanghai University of Engineering Science
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Shanghai University of Engineering Science
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Abstract

The invention discloses a magnetic nano composite material and a preparation method and application thereof. The magnetic nano composite material is obtained by firstly coating ferroferric oxide with silicon dioxide to obtain Fe3O4 @ SiO2 magnetic nano microspheres, then sequentially coating the surfaces of the Fe3O4 @ SiO2 magnetic nano microspheres with chitosan, triethylene tetramine and graphene oxide layer by layer. Experiments indicate that the magnetic nano composite material has large specific surface area, good morphology structure, strong magneticity, good adsorptive property and other advantages, can be used as a heavy metal ion and organic dye adsorbent and has a good use value and an application prospect in the environment, water treatment and other fields.

Description

A kind of magnetic nanometer composite material and its preparation method and application
Technical field
The present invention relates to a kind of magnetic nanometer composite material and its preparation method and application, belong to nano material technology neck Domain.
Background technology
While rapid technological growth and people's quality of life improve, problem of environmental pollution is also more and more fiery, its reclaimed water Pollution is particularly acute.And the quality of water quality affects the physical condition of people closely.Existing sewage disposal technology have from Sub- exchange process, membrane filter method, electrochemical process, photocatalytic degradation method, biological degradation method, absorption method.Wherein absorption method is because of its efficiency High, simple to operate, cheap the advantages of, is as one of most common method in sewage disposal.But absorption method also exists at present inhales Attached capacity is low, reclaim the shortcomings of difficulty, poor selectivity, serious secondary pollution, is further applied this severely limits it, and solves The key of these problems is exactly to develop the adsorbent of function admirable.
Shitosan is a kind of environmentally friendly natural polymerses, with good film forming, biocompatibility, Biological degradability, also with excellent absorption property, can effectively improve the adsorption capacity and separating property of adsorbent.Graphene It is a kind of new carbon of excellent performance, with great specific surface area, with larger adsorption capacity and absorption property.Cause This, making adsorbent with shitosan and Graphene at present carries out the technology of sewage disposal, existing in-depth study extensively.It is Chinese special Sharp " a kind of preparation methods of graphene/chitosan adsorbent resin of CN201310434322.2 ", " CN201510858159.1 is a kind of Graphene oxide/chitosan microball and preparation method thereof ", " CN201610174840.9 graphene oxides/chitosan multi-porous compound Microballoon and its preparation method and application " etc. all reports application of the Graphene/chitosan absorbent in sewage disposal.
In recent years, magnetic separation technique has been applied in water treatment field, and it is by the effect of magnetic field force, to different magnetic A kind of technology that the material of property is separate." a kind of Zn ferrite@of CN201510513108.5 are chitosan/oxidized for Chinese patent Graphene composite material and its preparation method and application ", " a kind of graphene oxides of CN201610310180.2 and chitosan magnetic Preparation method and applications of compound " etc. are reported and are magnetized shitosan using magnetisable material, prepare chitosan magnetic, then With chitosan magnetic as matrix, Graphene is covalently bound to chitosan magnetic surface, prepares Graphene/shitosan magnetic and inhale Attached dose is used for sewage disposal.
Cause the factor of water pollution a lot, the wherein discharge of heavy metal wastewater thereby and the discharge of organic dye waste water is to cause Two big principal elements of current water pollution, and current Graphene/chitosan absorbent Function Class is relatively simple, generally only Can effectively adsorb the pollutant of one type, and current Graphene/its magnetic of shitosan magnetic adsorbent is relatively low, to metal The absorption property of ion especially heavy metal ion is relatively low, there is presently no can effectively process metallic wastewater and waste water from dyestuff simultaneously Graphene/shitosan class adsorbent relevant report.
The content of the invention
In view of the above-mentioned problems existing in the prior art, it is an object of the invention to provide a kind of magnetic nanometer composite material and its Preparation method and application, to expand species and the application of magnetic nanometer composite material.
For achieving the above object, the technical solution adopted by the present invention is as follows：
A kind of magnetic nanometer composite material, is to obtain Fe by coated with silica ferroso-ferric oxide first3O4@SiO2Magnetic Nano microsphere, then in Fe3O4@SiO2Magnetic Nano microsphere surface coats shitosan (abbreviation CS), triethylene tetramine layer by layer successively (abbreviation TETA), graphene oxide (abbreviation GO) are obtained, and are abbreviated as：Fe3O4@SiO2@CS-TETA-GO。
A kind of method for preparing magnetic nanometer composite material of the present invention, comprises the following steps：
A) ferriferrous oxide nano microballoon is prepared using solvent-thermal method；
B) useMethod obtains core shell structure in ferriferrous oxide nano microsphere surface coated silica Fe3O4@SiO2Magnetic Nano microsphere；
C) using silane coupler and chloroacetic acid to Fe3O4@SiO2Magnetic Nano microsphere surface carries out carboxylated and is modified, Obtain Fe3O4@SiO2- COOH composites, then use Euplotes woodruffi by chitosan crosslinked in Fe3O4@SiO2- COOH is multiple Condensation material surface, obtains Chitosan-coated Fe3O4@SiO2Composite, be abbreviated as：Fe3O4@SiO2@CS；
D) using epichlorohydrin (i.e. epoxychloropropane) to Fe3O4@SiO2@CS are modified treatment, are then grafted triethylene four Amine, obtains triethylene tetramine cladding Fe3O4@SiO2The composite of@CS, is abbreviated as：Fe3O4@SiO2@CS-TETA；
E) by amidation process, by Fe3O4@SiO2@CS-TETA are grafted to surface of graphene oxide, obtain graphite oxide Alkene coats Fe3O4@SiO2The composite of@CS-TETA, that is, obtain described magnetic nanometer composite material Fe3O4@SiO2@CS- TETA-GO。
Preferably, the step a) includes following operation：
By Iron(III) chloride hexahydrate, two citric acid monohydrate trisodiums and sodium acetate are scattered in ethylene glycol, are turned after stirring Move in reactor, then insulation reaction 7~15 hours at 150~300 DEG C, terminate reaction, Magneto separate, to the solid collected Washed, dried, that is, obtained described ferriferrous oxide nano microballoon.
As further preferred scheme, Iron(III) chloride hexahydrate：Two citric acid monohydrate trisodiums：The mass ratio of sodium acetate is (1 ~5)：(0.7~1)：(4~5).
Used as further preferred scheme, 1~5g ferric trichlorides use 60~80mL ethylene glycol.
Preferably, the step b) includes following operation：
Obtained ferriferrous oxide nano microballoon is scattered in alcohol-water mixture, ammoniacal liquor is added after ultrasound is uniform, then The lower alcoholic solution that tetraethyl orthosilicate is added dropwise of stirring, then reacts 10~18 hours at room temperature, terminates reaction, Magneto separate, to receiving The solid of collection is washed, dried, that is, obtain described Fe3O4@SiO2Magnetic Nano microsphere.
Used as further preferred scheme, alcoholic solvent used is ethanol.
Used as further preferred scheme, in alcohol-water mixture, alcoholic solvent is (80~100) with the volume ratio of water：(1~ 10)。
Used as further preferred scheme, in the alcoholic solution of tetraethyl orthosilicate, tetraethyl orthosilicate is with the volume ratio of alcoholic solvent 1:10~1:20.
Used as further preferred scheme, 100~120mg ferroso-ferric oxides need to use 1~8mL ammoniacal liquor and 100~500 μ L Tetraethyl orthosilicate.
Preferably, in the step c) carboxylated is modified to include following operation：
By obtained Fe3O4@SiO2Magnetic Nano microsphere is scattered in alcohol-water mixture, and silane idol is added after ultrasound is uniform Connection agent APTES (chemical name is aminopropyl triethoxysilane), then insulation reaction 7~15 hours at 45~55 DEG C, tie Shu Fanying, separation of solid and liquid is scattered in the alcoholic solution of chloroacetic acid again after the solid washing isolated, regulation reaction solution PH value is reacted 7~15 hours to 7.5~8.5, then at 75~85 DEG C, terminates reaction, and Magneto separate, the solid to collecting is washed Wash, dry, that is, obtain described Fe3O4@SiO2- COOH composites.
As further preferred scheme, 150~300mg Fe3O4@SiO2Magnetic Nano microsphere needs to use 1~3mL APTES and 5~15mL chloroacetic acids.
Used as further preferred scheme, alcoholic solvent is ethanol；Alcoholic solvent and the volume ratio of water are 30 in alcohol-water mixture:1 ~50:1；Alcoholic solvent and the volume ratio of chloroacetic acid are 5 in the alcoholic solution of chloroacetic acid:1~1:1.
Preferably, the Euplotes woodruffi in the step c) includes following operation：
Dissolve the chitosan in 2~8wt% acetic acid solutions, be subsequently adding Fe3O4@SiO2- COOH composites, in room The lower reaction of temperature 7~15 hours, terminates reaction, and Magneto separate, the solid isolated is scattered in 2~8wt% acetic acid solutions again, plus Enter 25wt% glutaraldehydes, in stirring reaction 3~5 hours at 30~70 DEG C, terminate reaction, Magneto separate, the solid to collecting is carried out Wash, dry, that is, obtain described Fe3O4@SiO2@CS。
Used as further preferred scheme, 80~150mg shitosans are dissolved in 10~20mL acetic acid solutions.
As further preferred scheme, 5~15mg Fe3O4@SiO2- COOH composites need to use 80~150mg shells Glycan and 0.1~1mL glutaraldehydes.
Preferably, the step d) includes following operation：
By Fe3O4@SiO2@CS are scattered in isopropanol, in being stirred 0.5~1.5 hour at 35~45 DEG C, are subsequently adding table chlorine Alcohol, insulation reaction 7~15 hours terminates reaction, and Magneto separate is scattered in N, N- dimethyl methyls again after the solid washing isolated In acid amides, stirring reaction 0.5~1.5 hour at 45~60 DEG C is subsequently adding trien, and insulation reaction 3~5 is small When, terminating reaction, Magneto separate, the solid to collecting is washed, dried, that is, obtain described Fe3O4@SiO2@CS-TETA。
As further preferred scheme, 450~600mg Fe3O4@SiO2@CS need to use 40~80mL isopropanols, 5~ 15mL epichlorohydrins, 20~40mL N,N-dimethylformamides and 10~30mL triens.
Preferably, the step e) includes following operation：
Graphene oxide is dispersed in water, ultrasound is uniform, (chemical name is 1- ethyls-(3- dimethylaminos to add EDC Base propyl group) carbodiimide hydrochloride) and NHS (chemical name is N-hydroxy-succinamide), regulation solution to neutrality, add Fe3O4@SiO2@CS-TETA, then stirring reaction 2~3 hours at 60~70 DEG C, terminate reaction, and Magneto separate is consolidated to collection Body is washed, dried, that is, obtain described magnetic nanometer composite material Fe3O4@SiO2@CS-TETA-GO。
As further preferred scheme, graphene oxide and Fe3O4@SiO2The mass ratio of@CS-TETA is (6~10)：(15 ~25).
As further preferred scheme, graphene oxide：EDC：The mass ratio of NHS is (60~100)：(1~8)：(1~ 5)。
Magnetic nanometer composite material of the present invention can be used as the adsorbent of heavy metal ion, be particularly used as copper ion Adsorbent.
Magnetic nanometer composite material of the present invention also acts as the adsorbent of organic dyestuff, is particularly used as methylene Blue adsorbent.
Compared with prior art, the present invention has following conspicuousness beneficial effect：
1st, the present invention obtains Fe first by coated with silica ferroso-ferric oxide3O4@SiO2Magnetic Nano microsphere, then In Fe3O4@SiO2Cladding shitosan, triethylene tetramine, graphene oxide obtain nucleocapsid knot layer by layer successively on magnetic Nano microsphere surface The magnetic nanometer composite material Fe of structure3O4@SiO2@CS-TETA-GO；After tested：Magnetic Nano composite wood provided by the present invention Material Fe3O4@SiO2@CS-TETA-GO have the advantages that specific surface area is big, appearance structure is good, relatively high magnetism, good adsorption performance, Especially both adsorbable metal ion or adsorbable organic dyestuff, adsorption capacity big (to the methyl blue and copper ion in water most Big adsorbance respectively reaches 529.10mg/g and 324.68mg/g), and can reach adsorption equilibrium in 20 minutes, in environment, Shui Chu The fields such as reason have preferable use value and application prospect；
2nd, the present invention uses cladding process layer by layer, successively in Fe3O4@SiO2Surface coating shitosan, triethylene tetramine, oxidation Graphene, compared to traditional one kettle way cross-linked chitosan and graphene oxide for, the shell that can be evenly coated in material surface Glycan layer and graphene oxide layer, it is to avoid shitosan, graphene oxide molecule self-crosslinking, preparation process are controllable, technique letter Single, the particle size of nano-particle can be adjusted by changing the size of ferroso-ferric oxide core, and green is gentle, environment-friendly, keep away Exempt from secondary pollution, and the product stable appearance for preparing, be adapted to large-scale production.
Brief description of the drawings
Fig. 1 is the Fe prepared in embodiment3O4、Fe3O4@SiO2、Fe3O4@SiO2@CS and Fe3O4@SiO2@CS- The scanning electron microscope (SEM) photograph and transmission electron microscope picture of TETA-GO；
Fig. 2 is the Fe prepared in embodiment3O4、Fe3O4@SiO2、Fe3O4@SiO2@CS and Fe3O4@SiO2@CS- The magnetic hysteresis response curve of TETA-GO；
Fig. 3 is the Fe prepared in embodiment3O4、Fe3O4@SiO2、Fe3O4@SiO2@CS and Fe3O4@SiO2@CS- The X-ray diffracting spectrum of TETA-GO；
Fig. 4 be in application examples 1 magnetic nanometer composite material to the adsorption capacity of methylene blue and copper ion with pH change Curve；
Fig. 5 be application examples 2 in magnetic nanometer composite material to methylene blue and the isothermal adsorption figure of copper ion；
Fig. 6 be application examples 3 in magnetic nanometer composite material to methylene blue and the circulation absorption design sketch of copper ion.
Specific embodiment
Technical solution of the present invention is described in further detail and completely with reference to embodiment and application examples.
Embodiment
First, the preparation of ferriferrous oxide nano microballoon：
3.13g Iron(III) chloride hexahydrates, 0.81g two citric acid monohydrate trisodiums are added in 70mL ethylene glycol, at room temperature Stirring to it is complete it is molten after, add 4.81g sodium acetates, continue to stir to it is molten it is clear after be transferred in reactor, be then incubated at 280 DEG C Reaction 10 hours, terminates reaction, and Magneto separate, the solid to collecting is washed with deionized to neutrality, then dries, that is, obtain institute The ferriferrous oxide nano microballoon stated, it is standby.
2nd, Fe3O4@SiO2The preparation of magnetic Nano microsphere：
Ferriferrous oxide nano microballoon obtained in 0.12g is scattered in 102mL ethanol waters (96mL ethanol+6mL water) In, ultrasound adds 3mL ammoniacal liquor after making to be uniformly dispersed within 20 minutes, then stirs lower ethanol solution (300 μ that tetraethyl orthosilicate is added dropwise LTEOS is scattered in 5mL ethanol and obtains), reaction, Magneto separate, to the solid collected are terminated in room temperature reaction 15 hours after completion of dropping Washed with water and ethanol respectively successively, then dried, that is, obtained described Fe3O4@SiO2Magnetic Nano microsphere, it is standby.
3rd, Fe3O4@SiO2The preparation of@CS composites：
1) by Fe obtained in 0.22g3O4@SiO2Magnetic Nano microsphere be scattered in 92mL ethanol water (90mL ethanol+ 2mL water) in, 1.8mL silane coupling As PTES is slowly added dropwise after ultrasound is uniform, and (chemical name is aminopropyl-triethoxy silicon Alkane), then insulation reaction 10 hours at 50 DEG C, terminate reaction, separation of solid and liquid, and the solid isolated is heavy after washing three times with water Newly it is scattered in the ethanol solution of chloroacetic acid (chlorethanol+30mL ethanol of 10mL mono-), adjusts the pH value of reaction solution to 8,80 Reacted 10 hours at DEG C, terminate reaction, Magneto separate, the solid to collecting is washed with water and ethanol respectively successively, Ran Hougan It is dry, that is, obtain described Fe3O4@SiO2- COOH composites, it is standby；
2) 0.11g shitosans are scattered in 15mL, 5wt% acetic acid solution, are stirred at 40 DEG C to complete molten, Ran Houjia Enter 0.01gFe3O4@SiO2- COOH composites, room temperature reaction 12 hours terminates reaction, and Magneto separate is gathered with removing unnecessary shell Sugar, the solid isolated is scattered in 15mL, 5wt% acetic acid solution again, 0.5mL, 25wt% glutaraldehyde is slowly added dropwise, in 60 Stirring reaction 3 hours at DEG C, terminate reaction, and Magneto separate, the solid to collecting is washed with water and ethanol respectively successively, then Dry, that is, obtain described Fe3O4@SiO2@CS composites, it is standby.
4th, Fe3O4@SiO2The preparation of@CS-TETA composites：
By Fe obtained in 0.31g3O4@SiO2@CS are scattered in 50mL isopropanols, in being stirred 1 hour at 40 DEG C, are subsequently adding 10mL epichlorohydrins, insulation reaction 10 hours terminates reaction, Magneto separate, and the solid isolated is washed with deionized to remove not It is scattered in again in 30mL DMFs after the epichlorohydrin of reaction, stirring reaction 1 hour, Ran Houjia at 50 DEG C Enter 20mL triens, insulation reaction 4 hours terminates reaction, and Magneto separate, the solid to collecting uses water and second respectively successively Alcohol is washed, and is then dried, that is, obtain described Fe3O4@SiO2@CS-TETA composites, it is standby.
5th, magnetic nanometer composite material Fe3O4@SiO2The preparation of@CS-TETA-GO：
0.08g graphene oxides are scattered in 300mL water, ultrasound is uniform, (chemical name is 1- to add 3.80g EDC Ethyl-(3- dimethylaminopropyls) carbodiimide hydrochloride) and 2.32g NHS (chemical name is that N- hydroxysuccinimidyls acyl is sub- Amine), solution is adjusted to neutrality and in 2 hours (with the carboxyl on graphene oxide that deactivates) is stirred at 40 DEG C, it is subsequently adding 0.02gFe3O4@SiO2@CS-TETA, then stirring reaction 2 hours at 65 DEG C, terminate reaction, Magneto separate, to the solid collected Washed with water and ethanol respectively successively, then dried, that is, obtained described magnetic nanometer composite material Fe3O4@SiO2@CS- TETA-GO。
Fig. 1 is the Fe prepared in embodiment3O4、Fe3O4@SiO2、Fe3O4@SiO2@CS and Fe3O4@SiO2@CS- The scanning electron microscope (SEM) photograph and transmission electron microscope picture of TETA-GO, wherein a, b, c, d respectively are Fe3O4、Fe3O4@SiO2、Fe3O4@ SiO2@CS、Fe3O4@SiO2The scanning electron microscope (SEM) photograph of@CS-TETA-GO；E, f, g, h respectively are Fe3O4、Fe3O4@SiO2、 Fe3O4@SiO2@CS、Fe3O4@SiO2The transmission electron microscope picture of@CS-TETA-GO；From Fig. 1 (a-d), using described in the present embodiment Preparation method, can obtain the Fe that size is homogeneous, surface is smooth, appearance structure is good3O4、Fe3O4@SiO2、Fe3O4@SiO2@CS and Fe3O4@SiO2@CS-TETA-GO；From Fig. 1 (e-h), using preparation method described in the present embodiment, load can be obtained equal The even, Fe that overall appearance structure is good3O4@SiO2@CS-TETA-GO nano materials, and silica, shitosan, graphite oxide Alkene is to be coated on Fe layer by layer3O4Surface, and be evenly coated；From transmission electron microscope picture as can be seen that silicon dioxide layer in the present embodiment Thickness be about between 50~60nm, the thickness of the silicon dioxide layer can add the amount of TEOS freely adjust by changing； Similarly, the shitosan of load, graphene oxide layer thickness can also by add shitosan, graphene oxide amount come freedom Regulation.
Fig. 2 is the Fe prepared in embodiment3O4、Fe3O4@SiO2、Fe3O4@SiO2@CS and Fe3O4@SiO2@CS- The magnetic hysteresis response curve of TETA-GO, wherein a, b, c, d respectively is Fe3O4@SiO2@CS-TETA-GO、Fe3O4@SiO2@CS、 Fe3O4@SiO2、Fe3O4, it can be seen that using Fe manufactured in the present embodiment3O4@SiO2@CS-TETA-GO have excellent surpassing Paramagnetism, as adsorbent using can well realize separation of solid and liquid and recycling.
Fig. 3 is the Fe prepared in embodiment3O4、Fe3O4@SiO2、Fe3O4@SiO2@CS and Fe3O4@SiO2@CS- The X-ray diffracting spectrum of TETA-GO；Wherein a, b, c, d respectively are Fe3O4@SiO2@CS-TETA-GO、Fe3O4@SiO2@ CS、Fe3O4@SiO2、Fe3O4, it can be seen that with silica, shitosan, graphene oxide cladding layer by layer, be prepared into The peak intensity of the nano material XRD spectrum for arriving is stronger and narrower, illustrates that the magnetic of magnetic Nano material also increases therewith.
Application examples 1
Absorption property is investigated under condition of different pH：
The initial concentration of methylene blue and copper ion is all 500mg/L；According to methylene blue and copper ion under different pH Stability, set methylene blue (abbreviation MB) pH test scopes be 2-10；The pH test scopes of copper ion are 2-6；Respectively The methylene blue and copper ion solution 20mL of 500mg/L are taken in centrifuge tube, the Fe of 20mg embodiments preparation is added3O4@SiO2@ It is put into after CS-TETA-GO in water bath chader and is shaken 24 hours at 25 DEG C；After the completion of absorption, the concentration of remaining methylene blue is used Ultraviolet specrophotometer is tested, and the concentration of remaining copper ion is tested with ICP plasma atomic emission spectrometers；Testing result is detailed As shown in Figure 4.
Fig. 4 is Fe3O4@SiO2@CS-TETA-GO are to the adsorption capacity of methylene blue and copper ion with pH change curves；From It is visible in figure, Fe manufactured in the present embodiment3O4@SiO2@CS-TETA-GO acid resistances are good, to methylene under the conditions of pH wider Blue and copper ion all has excellent suction-operated, wherein the adsorbance in pH=6 to copper ion is maximum, in pH=10 pair The adsorbance of methylene blue is maximum.
Application examples 2
Isothermal adsorption Performance：
The initial concentration scope of methylene blue is set to 50~1000mg/L；The initial concentration scope of copper ion is set to 50~ 500mg/L；Both absorption pH value are set to 10,6 respectively；Adsorption time is set to 24 hours；25 DEG C of adsorption temp；Absorption is completed Afterwards, the concentration of remaining methylene blue is tested with ultraviolet specrophotometer, and the concentration of remaining copper ion is sent out with ICP Plasma-Atomics Penetrate spectrometer test；Testing result is detailed as shown in Figure 5.
Fig. 5 is Fe3O4@SiO2@CS-TETA-GO are to methylene blue and the isothermal adsorption figure of copper ion；It can be seen that this Fe prepared by embodiment3O4@SiO2There is@CS-TETA-GO excellent isothermal adsorption to act on to methylene blue and copper ion, its Methylene Blue reaches adsorption equilibrium in 900mg/L；Copper ion reaches adsorption equilibrium in 500mg/L.
Application examples 3
Circulation absorption Performance：
After isothermal adsorption terminates, by Fe3O4@SiO2It is vacuum dried after@CS-TETA-GO centrifuge washings, is circulated for adsorbing Methylene blue and copper ion, to detect that it recycles activity；Testing result is detailed as shown in Figure 6.
Fig. 6 is Fe3O4@SiO2@CS-TETA-GO are to methylene blue and the circulation absorption design sketch of copper ion.Can from figure See, Fe3O4@SiO2After@CS-TETA-GO recycle 6 times, the adsorption rate to methylene blue and copper ion is not changed in substantially, Illustrate that there is excellent absorption property.
Finally need it is pointed out here that be：The above is only part preferred embodiment of the invention, it is impossible to be interpreted as to this hair The limitation of bright protection domain, those skilled in the art's the above of the invention make some it is nonessential improvement and Adjustment belongs to protection scope of the present invention.

Claims (10)

1. a kind of magnetic nanometer composite material, it is characterised in that：It is that Fe is obtained by coated with silica ferroso-ferric oxide first3O4@ SiO2Magnetic Nano microsphere, then in Fe3O4@SiO2Magnetic Nano microsphere surface coats shitosan, triethylene four layer by layer successively Amine, graphene oxide are obtained, and are abbreviated as：Fe3O4@SiO2@CS-TETA-GO。
2. a kind of method of the magnetic nanometer composite material prepared described in claim 1, it is characterised in that comprise the following steps：
A) ferriferrous oxide nano microballoon is prepared using solvent-thermal method；
B) useMethod obtains the Fe of core shell structure in ferriferrous oxide nano microsphere surface coated silica3O4@SiO2 Magnetic Nano microsphere；
C) using silane coupler and chloroacetic acid to Fe3O4@SiO2Magnetic Nano microsphere surface carries out carboxylated and is modified, and obtains Fe3O4@SiO2- COOH composites, then use Euplotes woodruffi by chitosan crosslinked in Fe3O4@SiO2- COOH composite woods Material surface, obtains Chitosan-coated Fe3O4@SiO2Composite, be abbreviated as：Fe3O4@SiO2@CS；
D) using epichlorohydrin to Fe3O4@SiO2@CS are modified treatment, are then grafted triethylene tetramine, obtain triethylene tetramine Cladding Fe3O4@SiO2The composite of@CS, is abbreviated as：Fe3O4@SiO2@CS-TETA；
E) by amidation process, by Fe3O4@SiO2@CS-TETA are grafted to surface of graphene oxide, obtain graphene oxide bag Cover Fe3O4@SiO2The composite of@CS-TETA, that is, obtain described magnetic nanometer composite material Fe3O4@SiO2@CS-TETA- GO。
3. method as claimed in claim 2, it is characterised in that the step a) includes following operation：
Iron(III) chloride hexahydrate, two citric acid monohydrate trisodiums and sodium acetate are scattered in ethylene glycol, are transferred to after stirring In reactor, then insulation reaction 7~15 hours at 150~300 DEG C, terminate reaction, and Magneto separate, the solid to collecting is carried out Wash, dry, obtain final product described ferriferrous oxide nano microballoon.
4. method as claimed in claim 2, it is characterised in that the step b) includes following operation：
Obtained ferriferrous oxide nano microballoon is scattered in alcohol-water mixture, ammoniacal liquor is added after ultrasound is uniform, then stirred The lower alcoholic solution that tetraethyl orthosilicate is added dropwise, then reacts 10~18 hours at room temperature, terminates reaction, Magneto separate, to what is collected Solid is washed, dried, and obtains final product described Fe3O4@SiO2Magnetic Nano microsphere.
5. method as claimed in claim 2, it is characterised in that carboxylated in step c) is modified to include following operation：
By obtained Fe3O4@SiO2Magnetic Nano microsphere is scattered in alcohol-water mixture, and silane coupler is added after ultrasound is uniform APTES, then insulation reaction 7~15 hours at 45~55 DEG C, terminate reaction, separation of solid and liquid, after the solid washing isolated Again it is scattered in the alcoholic solution of chloroacetic acid, the pH value for adjusting reaction solution reacts 7 to 7.5~8.5, then at 75~85 DEG C ~15 hours, terminate reaction, Magneto separate, the solid to collecting is washed, dried, and obtains final product described Fe3O4@SiO2- COOH is multiple Condensation material.
6. method as claimed in claim 2, it is characterised in that the Euplotes woodruffi in step c) includes following operation：
Dissolve the chitosan in 2~8wt% acetic acid solutions, be subsequently adding Fe3O4@SiO2- COOH composites, at room temperature Reaction 7~15 hours, terminates reaction, and Magneto separate, the solid isolated is scattered in 2~8wt% acetic acid solutions again, adds 25wt% glutaraldehydes, in stirring reaction 3~5 hours at 30~70 DEG C, terminate reaction, and Magneto separate, the solid to collecting is washed Wash, dry, obtain final product described Fe3O4@SiO2@CS。
7. method as claimed in claim 2, it is characterised in that the step d) includes following operation：
By Fe3O4@SiO2@CS are scattered in isopropanol, in being stirred 0.5~1.5 hour at 35~45 DEG C, are subsequently adding epichlorohydrin, protect Temperature reaction 7~15 hours, terminates reaction, and Magneto separate is scattered in DMF again after the solid washing isolated In, stirring reaction 0.5~1.5 hour at 45~60 DEG C is subsequently adding trien, insulation reaction 3~5 hours, knot Shu Fanying, Magneto separate, the solid to collecting is washed, dried, and obtains final product described Fe3O4@SiO2@CS-TETA。
8. method as claimed in claim 2, it is characterised in that the step e) includes following operation：
Graphene oxide is dispersed in water, ultrasound is uniform, adds EDC and NHS, regulation solution to neutrality to add Fe3O4@ SiO2@CS-TETA, then stirring reaction 2~3 hours at 60~70 DEG C, terminate reaction, and Magneto separate, the solid to collecting enters Row is washed, dried, and obtains final product described magnetic nanometer composite material Fe3O4@SiO2@CS-TETA-GO。
9. the application of the magnetic nanometer composite material described in a kind of claim 1, it is characterised in that：It is multiple with described magnetic Nano Condensation material is used as the adsorbent of heavy metal ion.
10. the application of the magnetic nanometer composite material described in a kind of claim 1, it is characterised in that：Described magnetic Nano is answered Condensation material is used as the adsorbent of organic dyestuff.
CN201710079429.8A 2017-02-14 2017-02-14 Magnetic nano composite material and a preparation method and application thereof Pending CN106693920A (en)

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107721057A (en) * 2017-10-25 2018-02-23 镇江市丹徒区华发五金有限公司 A kind of method for treating copper-containing waste water based on magnetic adsorbent
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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102489300A (en) * 2011-11-18 2012-06-13 东华大学 Preparation method for magnetic nanometer microballoon photocatalysis composite materials
WO2012028964A3 (en) * 2010-09-03 2013-07-04 Indian Institute Of Technology Reduced graphene oxide-based-composites for the purification of water
CN105597658A (en) * 2015-10-13 2016-05-25 浙江师范大学 Magnetic nano-silica and graphene composite material, and preparation method and application thereof

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2012028964A3 (en) * 2010-09-03 2013-07-04 Indian Institute Of Technology Reduced graphene oxide-based-composites for the purification of water
CN102489300A (en) * 2011-11-18 2012-06-13 东华大学 Preparation method for magnetic nanometer microballoon photocatalysis composite materials
CN105597658A (en) * 2015-10-13 2016-05-25 浙江师范大学 Magnetic nano-silica and graphene composite material, and preparation method and application thereof

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
BINYAN HUANG ET AL.: "Effect of Cu(II) ions on the enhancement of tetracycline adsorption by Fe3O4@SiO2-Chitosan/graphene oxide nanocomposite", 《CARBOHYDRATE POLYMERS》 *
HUACAI GE ET AL.: "Microwave preparation of triethylenetetramine modified graphene oxide/chitosan composite for adsorption of Cr(VI)", 《CARBOHYDRATE POLYMERS》 *

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