CN106540658B - A kind of graphene oxide covalent bond coated magnetic nano composition and preparation method thereof - Google Patents
A kind of graphene oxide covalent bond coated magnetic nano composition and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a kind of graphene oxide covalent bond coated magnetic nano compositions and preparation method thereof.The preparation method passes through preparation Fe3O4Nanoparticle, then to Fe3O4Nanoparticle carries out surface modification and introduces functional group, generates Fe3O4@SiO2‑NH2Particle, then react with graphene oxide, thus in Fe3O4@SiO2‑NH2Particle surface has coated the graphene oxide by being covalently keyed.The composite material and reported graphene oxide-Fe3O4Composite material is compared, and structure is improved, and stability greatly enhances, and overcomes graphene oxide electrostatic cladding Fe3O4And Fe3O4It is deposited on the defect of graphene oxide layer composite material.Graphene oxide-Fe prepared by this method3O4Composite material has excellent absorption property to heavy metal, and reusable, and adsorption process is simple, environmentally protective, has a wide range of application prospect in fields such as heavy metal-polluted water process.
Description
Technical field
The invention belongs to Carbon Materials technical fields, receive more particularly, to a kind of graphene oxide covalent bond coated magnetic
Rice corpuscles composite material and preparation method.
Background technique
Graphene is a kind of Novel Carbon Nanomaterials, just fast once appearance due to its unique structure and excellent performance
Short-term training is the focus of international field of new materials research.As water process adsorbent material, the application prospect of grapheme material is worth the phase
To.On the one hand be it have two-dimensional planar structure, the pore structure of opening, good flexibility, high mechanical strength and
Outstanding advantages of chemical property stabilization, large specific surface area；On the other hand, the carbon nano-tube material similar with graphene-structured performance
Good absorption property is gone out, and graphene, compared with carbon nanotube, specific surface area is bigger, and has been easier to carry out the regulation of structure
And design, therefore, graphene is just becoming the research hotspot of related fields as the research of adsorbent material in recent years.
Existing research proves that graphite alkenes material has good absorption property, but graphene or graphite oxide to heavy metal
Alkene material tends to that the aggregation of lamella occurs and reduces its performance in the solution, and adsorbs graphene material after heavy metal ion
Material is difficult to separate from solution.
Magnetic Nano material Fe3O4There is stronger absorption property to heavy metal and be easy preparation, it is often more important that it has
It is magnetic and separates quick and easy feature, this just compensates for the shortcomings that grapheme material difficulty separates, graphene-Fe3O4It is compound
Material adsorbs the Fe in the separation of heavy metal ion later period due to superparamagnetism3O4The introducing of nanoparticle need to only be placed in externally-applied magnetic field
In can realize separation easily.In addition, graphene-Fe3O4Have the further advantage that Fe3O4Nanoparticle easy in the solution
It is poly-, and can effectively prevent the aggregation of nano particle with the compound rear graphene sheet layer of graphene, chemical stability greatly enhances, together
When, graphene is also because of Fe3O4Barrier the structure of graphite is formed without accumulating again.
In recent years, graphene-Fe3O4The research of composite material has been achieved for biggish progress, at present it has been reported that various
Method such as solvothermal method, hydrothermal reduction method, one-step method, self-assembly method prepare graphene magnetic composite, composite wood
Material is not only applicable to the heavy metal ion such as absorption As, Co, Cr, Eu, and can also be used to handle methylene blue, rhodamine B, the Congo
The red equal organic matters such as organic dyestuff and protein.But in these graphene composite materials, Fe3O4Nanoparticle is mostly deposited on
In the level of graphene, it is considered that the oxygen atom in graphene face is Fe3O4The center of nucleation, oxygen atom and Fe3O4Only by quiet
Electric attraction or physical absorption, there are Fe3O4The problem of falling off from graphene.Fe in such composite material3O4It is not very steady
Fixed, the heavy metal ion being on the one hand adsorbed is also likely to occupy oxygen atom position on graphene oxide, leads to heavy metal ion
And Fe3O4There is competition in particle, may make Fe on occupying graphene oxide oxygen atom position3O4It is detached from original nucleation site,
The structure and performance of composite material so are inevitably affected, moreover in adsorption-desorption regenerative process, often adjoint
Strong mechanical agitation process, so as to make Fe3O4It is detached from graphene surface, and also results in Fe3O4In certain journey
There are agglomeration traits on degree.In recent years, it has tried to and prepares graphene oxide electrostatic cladding Fe3O4Nanocomposites material
Material (a kind of preparation method of hud typed ferroso-ferric oxide/graphene oxide composite nano catalyst, application number:
201610310844.5), but such composite material as adsorbent absorption heavy metal ion have obvious shortcoming, due to graphite oxide
Alkene is by electrostatic attraction and Fe3O4Connection, thus in regenerative process, under condition of different pH, electrostatic attraction will subtract significantly
It is weak, Fe is detached from so as to cause the graphene oxide of cladding3O4, composite material, which occurs to disintegrate, declines its absorption property, final to influence
Its application value.
Summary of the invention
In view of the problems of the existing technology, the technical problem to be solved in the present invention is to provide a kind of graphene oxide is covalent
The preparation method of key coated magnetic nano composition.
Another object of the present invention is to provide kind of a graphene oxide covalent bond coated magnetic nano compositions, should
Composite material has stable structure, has excellent absorption property, especially its regenerative adsorption ability excellent heavy metal ion
It is good.
The purpose of the present invention is achieved by the following technical programs:
A kind of preparation method of graphene oxide covalent bond coated magnetic nano composition, including following step are provided
It is rapid:
S1. polyethylene glycol is added in ethylene glycol, is made it dissolve under 80 DEG C of stirring conditions, by Iron(III) chloride hexahydrate
It is added in above-mentioned lysate with Sodium acetate trihydrate, stirring makes it completely dissolved, and in course of dissolution, steams to mixed solution and dripping
Distilled water adjusts mixed liquid concentration, is transferred in autoclave, autoclave is put into 200 DEG C of air dry oven later
It reaction a period of time, is cooled to room temperature, resulting product is collected by centrifugation, wash drying, obtain Fe3O4Nanoparticle；
S2. by the resulting Fe of step S13O4Nanoparticle, which is added in dehydrated alcohol, forms mixed solution, ultrasonic disperse,
Ethyl orthosilicate is then added dropwise to mixing toward mixed solution and dripping ammonia spirit later in 30 DEG C of stirred in water bath
In liquid, products therefrom is carried out Magnetic Isolation, washs drying, obtain Fe by reaction a period of time3O4 @SiO2Particle；
S3. by the resulting Fe of step S23O4@SiO2Particle ultrasonic disperse to contain distilled water, isopropanol and 3- aminopropyl three
In the mixed liquor of Ethoxysilane, under nitrogen or argon atmosphere, certain time is reacted under 70 DEG C of stirring conditions, gained is produced
Object carries out Magnetic Isolation, washs drying, obtains the Fe of surface amination3O4 @SiO2Particle；
S4. by graphene oxide ultrasonic disperse in distilled water, and its pH value is adjusted to 5.0 ~ 6.0 with buffer solution, it
1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride and n-hydroxysuccinimide, stirring, ultrasound is added simultaneously afterwards
Afterwards, suspension is formed, by the Fe of surface amination made from step S33O4 @SiO2Particle is added in above-mentioned suspension, in 80
A period of time is reacted under DEG C stirring condition, and products therefrom is subjected to Magnetic Isolation, is washed 2 ~ 4 times with distilled water and dehydrated alcohol,
Then it is dried in vacuo at 60 DEG C, obtains graphene oxide covalent bond coated magnetic nano composition.
Preferably, step S1, washing drying process described in S2, S3 is alternately to be washed using distilled water and dehydrated alcohol
It washs, it is then dry at 60 DEG C.
Preferably, the molecular weight of polyethylene glycol described in step S1 is 2000 ~ 8000, and polyethylene glycol is with quality of glycol ratio
1:10 ~ 100, the distilled water of the dropwise addition and the volume ratio of ethylene glycol are 1:4 ~ 8, and the quality of Sodium acetate trihydrate is six hydration trichlorines
1.5 ~ 3.5 times for changing weight of iron, the quality of Iron(III) chloride hexahydrate is 1 ~ 2 times of polyethylene glycol quality.
It is further preferred that the molecular weight of polyethylene glycol described in step S1 is 4000 ~ 8000, polyethylene glycol and ethylene glycol matter
Amount is than being 1:40 ~ 100, and the distilled water of the dropwise addition and the volume ratio of ethylene glycol are 1:4 ~ 8, and the quality of Sodium acetate trihydrate is six water
2.7 ~ 3.5 times for closing ferric trichloride quality, the quality of Iron(III) chloride hexahydrate is 1.35 ~ 2 times of of polyethylene glycol quality
Preferably, step S1 mesohigh reaction kettle is put into the reaction time in 200 DEG C of air dry oven as 4 ~ 8h.
Preferably, Fe in mixed solution described in step S23O4Particle concentration is 2.5 ~ 10g/L, and the ammonia spirit concentration is
The volume ratio of 28wt%, the dehydrated alcohol and ammonium hydroxide is 20 ~ 100:1, the volume ratio of dehydrated alcohol and ethyl orthosilicate is 20 ~
100:1.
It is further preferred that Fe in mixed solution described in step S23O4Particle concentration is 5.0 ~ 10g/L, the ammonia spirit
Concentration is 28wt%, and the volume ratio of the dehydrated alcohol and ammonium hydroxide is 55 ~ 100:1, the volume ratio of dehydrated alcohol and ethyl orthosilicate
For 70 ~ 100:1.
Preferably, 6 ~ 8h is reacted after ethyl orthosilicate being added dropwise in mixed liquor described in step S2；Institute in step S3
State 6 ~ 8h of reaction under 70 DEG C of stirring conditions.
Preferably, the volume ratio of isopropanol and distilled water described in step S3 is 2 ~ 3:1, the volume ratio of isopropanol and APTES
For 20 ~ 80:1.
It is further preferred that the volume ratio of isopropanol described in step S3 and distilled water is 2.5 ~ 3:1, isopropanol and APTES
Volume ratio be 50 ~ 80:1.
Preferably, the quality of 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride described in step S4 is oxidation
The 25% ~ 100% of graphene quality, the quality of n-hydroxysuccinimide are the 20% ~ 80% of graphene oxide quality.
It is further preferred that the quality of 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride described in step S4
It is the 50% ~ 100% of graphene oxide quality, the quality of n-hydroxysuccinimide is the 40% ~ 80% of graphene oxide quality.
Preferably, 1 ~ 3h is reacted described in step S4 under 80 DEG C of stirring conditions.
Compared with the prior art, the beneficial effects of the present invention are:
(1) present invention proposes graphene oxide covalent bond coated magnetic nano composition, with existing oxidation stone
The composite material that black alkene electrostatic coated magnetic nanoparticle and magnetic nano-particle are deposited on graphene oxide layer is compared, structure
It is greatly improved, which has very strong stability, firm covalent especially in wider pH value range
Bond energy supports its structure well, makes its structure remained stable, thus its absorption property, particularly its absorption regeneration performance obtain
It greatly promotes.
(2) present invention coats Fe using graphene oxide covalent bond3O4Nanoparticle, compared with Fe3O4It is deposited on oxygen
Composite material is compared on graphite alkene lamella, avoids the Fe occurred in absorption/desorption process3O4Particle aggregation, the feelings such as fall off
Condition, and the reported graphene oxide composite material by electrostatic cladding, at lower pH, graphene oxide and magnetic Nano
The electrostatic of particle weakens significantly, it may occur that disintegrates, the present invention coats Fe using covalent bond3O4, the deficiency of electrostatic cladding is overcome,
Composite material is caused to be improved.
(3) graphene oxide covalent bond coated magnetic nano composition prepared by the present invention is to Pb(II) performance
Excellent absorption property is gone out, especially its regenerability is splendid, before the fields such as heavy metal-polluted water process are widely used
Scape.
(4) present invention parameters such as the amount of reagent of different ratio can be added by control to control final magnetic Nano
Size, pattern and the institutional framework of particle.
Detailed description of the invention
Fig. 1 is (A) of graphene oxide covalent bond coated magnetic nano composition prepared by the embodiment of the present invention 1
Electron scanning micrograph and (B) transmission electron micrograph.
Fig. 2 is that the embodiment of the present invention 1 prepares (a) graphite oxide, (b) Fe3O4, (c) Fe3O4@SiO2-NH2And it (d) aoxidizes
The infrared spectrogram of graphene covalent bond coated magnetic nano composition.
Fig. 3 is graphene oxide covalent bond coated magnetic nano composition C1s prepared by the embodiment of the present invention 1
X-ray photoelectron spectroscopy (XPS) figure.
Fig. 4 is pair of graphene oxide covalent bond coated magnetic nano composition prepared by the embodiment of the present invention 1
The adsorption capacity of Pb (II) with cycle-index variation diagram.
Fig. 5 is (A) of graphene oxide covalent bond coated magnetic nano composition prepared by the embodiment of the present invention 2
Electron scanning micrograph and (B) transmission electron micrograph.
Specific embodiment
The present invention is further illustrated combined with specific embodiments below.Following embodiments only for illustration, Bu Nengli
Solution is limitation of the present invention.Unless stated otherwise, raw material and equipment used in following embodiments are that this field routinely makes
Raw material and equipment.
Embodiment 1
S1. 1.0 g polyethylene glycol (PEG-4000) are added in 40 mL ethylene glycol (EG), magnetic force under 80 DEG C of oil bath heatings
30min to PEG-4000 is stirred all to dissolve.Weigh 1.35 g Iron(III) chloride hexahydrate (FeCL3•6H2O), 3.6 g sodium acetate
(NaAc 3H2O), it is added in above-mentioned lysate, stirring makes it completely dissolved, and in course of dissolution, steams to mixed solution and dripping
Distilled water 5mL.Continue to stir after 30min is completely dissolved to mixed liquor, transfer them to 100mL with polytetrafluoroethyllining lining not
It becomes rusty in steel autoclave, 8h, cooled to room temperature is reacted in 200 DEG C of air dry oven.Be collected by centrifugation, with distilled water and
Dehydrated alcohol washs for several times, finally, dry 6h at 60 DEG C, is made Fe3O4Nanoparticle；
S2. 1.4g Fe is weighed3O4Nanoparticle is added in the four-hole boiling flask containing 280mL dehydrated alcohol, ultrasonic disperse
Then the ammonium hydroxide (28wt%) of 5.0mL is added in 15min.Mechanical stirring 15min under 30 DEG C of heating water baths, then by the positive silicon of 4.0mL
Acetoacetic ester (TEOS) is added dropwise in mixed liquor.Entire reaction keeps mechanical stirring 8h.Product carries out Magnetic Isolation with magnet,
After distilled water and dehydrated alcohol washing for several times, Fe is made in 60 DEG C of dry 6h3O4 @SiO2Particle；
S3. by 1.0g Fe3O4 @SiO2Particle is added to the 3- containing 40mL distilled water, 100mL isopropanol and 2.0mL
In the four-hole boiling flask of aminopropyl triethoxysilane (APTES) mixed liquor, ultrasonic disperse 1h.It is continually fed into N2In the case where, 70
DEG C heating water bath, mild mechanical stir 6h.End product carries out Magnetic Isolation with magnet, and distilled water and dehydrated alcohol washing are for several times
Afterwards, the Fe of surface amination is made in 60 DEG C of dry 6h3O4 @SiO2Particle；
S4. 20mg graphene oxide is added in 60mL distilled water, ultrasonic 1h is evenly dispersed, and is adjusted with buffer solution
Playing pH is 5.5.Then 10mgEDC, 8mgNHS are added in above-mentioned solution simultaneously, mechanical stirring 30min, then ultrasound 30min,
Form uniform suspension.By the Fe of 20mg surface amination3O4 @SiO2Particle is added in above-mentioned suspension, ultrasonic treatment
30min.Then, mechanical stirring 1h in the case of 80 DEG C of oil bath heatings.It is each with alcohol and deionized water respectively by product Magnetic Isolation
Washing three times, is dried in vacuo 6h at 60 DEG C, obtains graphene oxide covalent bond coated magnetic nano composition.
Test result analysis is referring to Fig. 1 ~ Fig. 4:
Fig. 1 is (A) scanning electricity of the graphene oxide covalent bond coated magnetic nano composition of this test preparation
Sub- microscope photo and (B) transmission electron micrograph.
Fig. 2 is this test preparation (a) graphene oxide, (b) Fe3O4, (c) Fe3O4@SiO2-NH2And (d) graphite oxide
The infrared spectrogram of alkene covalent bond coated magnetic nano composition.
It can be clearly seen that graphene oxide is coated on the Fe being modified securely in Fig. 13O4Surface, connection type
Totally different with electrostatic cladding, the partial size of composite particles is in 200nm or so, the SiO of cladding2Thickness is in 30nm or so；From Fig. 2
It can be seen that carboxyl peak and Fe in graphite oxide3O4@SiO2-NH2Weaken or disappear significantly after the two reaction in middle amido peak.
Fig. 3 is graphene oxide covalent bond coated magnetic nano composition C1s prepared by the embodiment of the present invention 1
X-ray photoelectron spectroscopy (XPS) figure.It can be seen in figure 3 that combining at 284.9,286.1,287.1,288.3,289.3 eV of energy
It is the peak XPS of C=C, C-N, C-O, C=O and O-C=O respectively, the peak C=C is most strong, illustrates that carbon atom is mostly sp2Hydridization, this
Consistent with graphene-structured, the peak C-N is also relatively strong, illustrates there is a large amount of C-N key in the sample, and C-O, C=O and the peak O-C=O
Weaker, graphene oxide contains the oxygen-containing groups such as a large amount of C-O, C=O, O-C=O.
In conjunction with Fig. 1, Fig. 2, Fig. 3 demonstrate these oxygen-containing groups in graphene oxide with-NH2Amidation has occurred
Reaction, generates C-N key, so as to form the graphene oxide coated magnetic nano composition being covalently keyed.
Fig. 4 is the graphene oxide covalent bond coated magnetic nano composition of this test preparation to Pb (II)
Adsorption capacity with cycle-index variation diagram.As can see from Figure 4 after 5 times recycle, composite material is maintained about
90% or so adsorption capacity, it was demonstrated that the composite material has excellent power of regeneration (de- washing lotion is 0.01M HCL).
Embodiment 2
S1. 1.0 g polyethylene glycol (PEG-4000) are added in 40 mL ethylene glycol (EG), magnetic force under 80 DEG C of oil bath heatings
30min to PEG-4000 is stirred all to dissolve.Weigh 1.35 g Iron(III) chloride hexahydrate (FeCL36H2O), 3.6 g sodium acetate
(NaAc 3H2O), it is added in above-mentioned lysate, stirring makes it completely dissolved, and in course of dissolution, steams to mixed solution and dripping
Distilled water H2O 10mL.Continue to stir after 30min is completely dissolved to mixed liquor, transfer them in the band polytetrafluoroethylene (PTFE) of 100mL
In the stainless steel autoclave of lining, 4h, cooled to room temperature are reacted in 200 DEG C of air dry oven.It is collected by centrifugation, with steaming
Distilled water and dehydrated alcohol wash for several times, finally, dry 6h at 60 DEG C, is made Fe3O4Particle；
S2. 1.4g Fe is weighed3O4Ultrasonic 15min is distributed in the four-hole boiling flask containing 280mL dehydrated alcohol, then plus
Enter the ammonium hydroxide (28wt%) of 5.0mL.Mechanical stirring 15min under 30 DEG C of heating water baths, then by 4.0mL ethyl orthosilicate (TEOS)
It is added dropwise in mixed liquor.Entire reaction keeps mechanical stirring 6h.Product carries out Magnetic Isolation with magnet, distilled water and anhydrous
Ethanol washing for several times after, 60 DEG C of dry 6h, be made Fe3O4 @SiO2Particle；
S3. by 1.0g Fe3O4 @SiO2Ultrasonic 1h is distributed to containing 40mL distilled water, 100mL isopropanol and 2.0mL
In the four-hole boiling flask of 3- aminopropyl triethoxysilane (APTES) mixed liquor.It is continually fed into N2In the case where, 70 DEG C of water-baths add
Heat, mild mechanical stir 8h.End product carries out Magnetic Isolation with magnet, after distilled water and dehydrated alcohol wash for several times, 60 DEG C
Dry 6h, is made the Fe of surface amination3O4 @SiO2Particle；
S4. 20mg graphene oxide ultrasound 1h is dispersed in 60mL distilled water, and has adjusted pH with buffer solution
It is 5.5, then 10mgEDC, 8mgNHS is added in above-mentioned solution, mechanical stirring 30min, then ultrasound 30min simultaneously, is formed
Uniform suspension.By the Fe of 20mg amino functional3O4 @SiO2Particle is added in above-mentioned suspension, ultrasonic treatment
30min.Then, mechanical stirring 3h in the case of 80 DEG C of oil bath heatings.It is each with alcohol and deionized water respectively by product Magnetic Isolation
Washing three times, is dried in vacuo 6h at 60 DEG C, obtains graphene oxide covalent bond coated magnetic nano composition.
Test result analysis participates in Fig. 5:
Fig. 5 is that (A) of the graphene oxide covalent bond coated magnetic nano composition of this test preparation scans electricity
Sub- microscope photo and (B) transmission electron micrograph.It can be seen from the figure that graphene oxide be coated on and be modified
Fe3O4Surface, connection type and electrostatic cladding are totally different, this test and the difference of embodiment 1 are: multiple obtained by the present embodiment
The particle diameter of condensation material is in 500nm or so.
The absorption to Pb (II) of graphene oxide covalent bond coated magnetic nano composition prepared by embodiment 2
After ability is 5 times with cycle-index, the adsorption capacity of composite material is about the 85% of former adsorption capacity.
Embodiment 3 ~ 10
The preparation method of embodiment 3 ~ 6 is substantially the same manner as Example 1, and difference is as follows:
3 difference from Example 1 of embodiment is: in step sl, 2.0 g polyethylene glycol (PEG-2000) being added
In 80 mL ethylene glycol (EG), magnetic agitation 30min to PEG-2000 all dissolves under 80 DEG C of oil bath heatings.Weigh 2.0 g, six water
Close ferric trichloride (FeCL3•6H2O), 3.0 g sodium acetate (NaAc 3H2O), it is added in above-mentioned lysate, stirring keeps it completely molten
Solution, in course of dissolution, to mixed solution and dripping distilled water H2O 10mL。
4 difference from Example 1 of embodiment is: in step sl, 2.0 g polyethylene glycol (PEG-8000) being added
In 80 mL ethylene glycol (EG), magnetic agitation 30min to PEG-8000 all dissolves under 80 DEG C of oil bath heatings.Weigh 4.0 g, six water
Close ferric trichloride (FeCL3•6H2O), 14.0 g sodium acetate (NaAc 3H2O), it is added in above-mentioned lysate, stirring keeps it completely molten
Solution, in course of dissolution, to mixed solution and dripping distilled water H2O 10mL。
5 difference from Example 1 of embodiment is: in step s 2, weighing 0.7g Fe3O4Ultrasonic 15min is distributed to
In four-hole boiling flask containing 280mL dehydrated alcohol, the ammonium hydroxide (28wt%) of 2.8mL is then added.Machinery stirs under 30 DEG C of heating water baths
15min is mixed, then 2.8mL ethyl orthosilicate (TEOS) is added dropwise in mixed liquor.
6 difference from Example 1 of embodiment is: in step s 2, weighing 2.8g Fe3O4Ultrasonic 15min is distributed to
In four-hole boiling flask containing 280mL dehydrated alcohol, the ammonium hydroxide (28wt%) of 14.0mL is then added.It is mechanical under 30 DEG C of heating water baths
15min is stirred, then 14.0mL ethyl orthosilicate (TEOS) is added dropwise in mixed liquor.
7 difference from Example 1 of embodiment is: in step s3, by 1.0g Fe3O4 @SiO2Ultrasonic 1h is distributed to
Four mouthfuls of 3- aminopropyl triethoxysilane (APTES) mixed liquor containing 3.5mL distilled water, 100mL isopropanol and 1.25mL
In flask.
8 difference from Example 1 of embodiment is: in step s3, by 1.0g Fe3O4 @SiO2Ultrasonic 1h is distributed to
Four mouthfuls of burnings of 3- aminopropyl triethoxysilane (APTES) mixed liquor containing 50mL distilled water, 100mL isopropanol and 5.0mL
In bottle.
9 difference from Example 1 of embodiment is: in step s 4,20mg graphene oxide ultrasound 1h uniformly being divided
It dissipates in 60mL distilled water, and having adjusted pH with buffer solution is 5.5, is then added to 5mgEDC, 4mgNHS simultaneously above-mentioned
In solution, mechanical stirring 30min, then ultrasound 30min, form uniform suspension.
10 difference from Example 1 of embodiment is: in step s 4,20mg graphene oxide ultrasound 1h uniformly being divided
Dissipate in 60mL distilled water, and with buffer solution adjusted pH be 5.5, then by 20mgEDC, 16mgNHS simultaneously be added on
It states in solution, mechanical stirring 30min, then ultrasound 30min, forms uniform suspension.
3 ~ 10 gained composite particles partial size of embodiment respectively may be about 100nm, 350nm, 200nm, 350nm,
250nm、 400nm 、150nm 、400nm。
The infrared spectroscopy of 3 ~ 10 gained composite material of embodiment and the x-ray photoelectron spectroscopy (XPS) of C1s are substantially similar, oxidation
Carboxyl peak and Fe in graphite3O4@SiO2-NH2Weaken or disappear significantly after the two reaction in middle amido peak；It is also deposited in composite material
At the peak XPS of C=C, C-N, C-O, C=O and O-C=O, wherein the peak C=C is most strong, illustrates that carbon atom is mostly sp2Hydridization, with
Graphene-structured is consistent, and the peak C-N is also relatively strong, illustrates there is a large amount of C-N key in the sample, and C-O, C=O and the peak O-C=O compared with
Weak, graphene oxide contains the oxygen-containing groups such as a large amount of C-O, C=O, O-C=O.
In conclusion these oxygen-containing groups in embodiment 3 ~ 10 in graphene oxide with-NH2Amide has occurred
Change reaction, generates C-N key, form the graphene oxide coated magnetic nano composition being covalently keyed.
The graphene oxide covalent bond coated magnetic nano composition prepared in embodiment 3 ~ 10 to Pb (II)
Adsorption capacity with cycle-index be 5 times after, the adsorption capacity of 3 ~ 10 gained composite material of embodiment respectively may be about former adsorption energy
93%, 85%, 90%, 86%, 89%, 85%, 90%, the 84% of power, it was demonstrated that the composite material all has excellent power of regeneration, and generates
Composite material particle diameter it is smaller, composite material have more excellent power of regeneration.
Claims (6)
1. a kind of preparation method of graphene oxide covalent bond coated magnetic nano composition, which is characterized in that oxidation
Graphene is connected by covalent bond with magnetic nano-particle, is coated on the surface of magnetic nano-particle, the preparation method includes
Following steps:
S1. polyethylene glycol is added in ethylene glycol, is made it dissolve under 80 DEG C of stirring conditions, by Iron(III) chloride hexahydrate and three
Water acetic acid sodium is added in above-mentioned lysate, and stirring makes it completely dissolved, in course of dissolution, to mixed solution and dripping distilled water
Mixed liquid concentration is adjusted, is transferred in autoclave later, autoclave is put into 200 DEG C of air dry oven and is reacted
For a period of time, it is cooled to room temperature, resulting product is collected by centrifugation, wash drying, obtain Fe3O4Nanoparticle；The poly- second
The molecular weight of glycol is 2000~8000, and polyethylene glycol and quality of glycol ratio are 1:10~100, the distilled water of the dropwise addition with
The volume ratio of ethylene glycol is 1:4~8, and the quality of Sodium acetate trihydrate is 1.5~3.5 times of Iron(III) chloride hexahydrate quality, six water
The quality for closing ferric trichloride is 1~2 times of polyethylene glycol quality；
S2. by the resulting Fe of step S13O4Nanoparticle, which is added in dehydrated alcohol, forms mixed solution, ultrasonic disperse, past mixed
It closes in solution and ammonia spirit is added dropwise, later in 30 DEG C of stirred in water bath, then ethyl orthosilicate is added dropwise in mixed liquor,
6~8h is reacted, products therefrom is subjected to Magnetic Isolation, drying is washed, obtains Fe3O4@SiO2Particle；In the mixed solution
Fe3O4Particle concentration is 2.5~10g/L, and the ammonia spirit concentration is 28wt%, the volume ratio of the dehydrated alcohol and ammonium hydroxide
For 20~100:1, the volume ratio of dehydrated alcohol and ethyl orthosilicate is 20~100:1；
S3. by the resulting Fe of step S23O4@SiO2Particle ultrasonic disperse to contain three second of distilled water, isopropanol and 3- aminopropyl
In the mixed liquor of oxysilane, the volume ratio of the isopropanol and distilled water is 2~3:1, and the volume ratio of isopropanol and APTES are
20~80:1 reacts 6~8h under 70 DEG C of stirring conditions, products therefrom is carried out Magnetic Isolation under nitrogen or argon atmosphere,
Drying is washed, the Fe of surface amination is obtained3O4@SiO2Particle；
S4. by graphene oxide ultrasonic disperse in distilled water, and its pH value is adjusted to 5.0~6.0, Zhi Houtong with buffer solution
When be added 1- (3- dimethylamino-propyl) -3- ethyl-carbodiimide hydrochloride and n-hydroxysuccinimide, after stirring, ultrasound,
Suspension is formed, by the Fe of surface amination made from step S33O4@SiO2Particle is added in above-mentioned suspension, in 80 DEG C
A period of time is reacted under stirring condition, products therefrom is subjected to Magnetic Isolation, washs 2~4 times with distilled water and dehydrated alcohol, so
It is dried in vacuo at 60 DEG C afterwards, obtains graphene oxide covalent bond coated magnetic nano composition.
2. the preparation method of graphene oxide covalent bond coated magnetic nano composition according to claim 1,
It is characterized in that, step S1, washing drying process described in S2, S3 is alternately to be washed using distilled water and dehydrated alcohol, is then existed
It is dry at 60 DEG C.
3. the preparation method of graphene oxide covalent bond coated magnetic nano composition according to claim 1,
It is characterized in that, step S1 mesohigh reaction kettle is put into the reaction time in 200 DEG C of air dry oven as 4~8h.
4. the preparation method of graphene oxide covalent bond coated magnetic nano composition according to claim 1,
It is characterized in that, the quality of 1- described in step S4 (3- dimethylamino-propyl) -3- ethyl-carbodiimide hydrochloride is graphene oxide
The 25%~100% of quality, the quality of n-hydroxysuccinimide are the 20%~80% of graphene oxide quality.
5. the preparation method of graphene oxide covalent bond coated magnetic nano composition according to claim 1,
It is characterized in that, step S4 is set forth in 1~3h of reaction under 80 DEG C of stirring conditions.
6. the graphene oxide covalent bond cladding that preparation method described in a kind of any one according to claim 1~5 is prepared
Magnetic nano-particle composite material.
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