CN106345414A - Magnetic core-shell nanocomposite as well as preparation method and application thereof - Google Patents
Magnetic core-shell nanocomposite as well as preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses a magnetic core-shell nanocomposite as well as a preparation method and application thereof. In the composite, graphene oxide is used as a matrix, and the surface of the matrix is loaded with Fe3O4@SiO2 nanoparticles through the effect of chitosan. The nanocomposite is prepared by the following steps: firstly, preparing Fe3O4 nanoparticles before Fe3O4@SiO2 nanoparticles; then, preparing graphene oxide by a Hummers method; and finally, loading the Fe3O4@SiO2 nanoparticles on the surface of graphene oxide through chitosan under the crosslinking effect of glutaraldehyde by a one-pot method. The nanocomposite realizes a good adsorption effect on antibiotics in wastewater and is convenient for recycling.
Description
Technical field
The invention belongs to environment functional material and water process new technical field are and in particular to a kind of magnetic core-shell is nano combined
Material and preparation method thereof and purposes.
Background technology
Tetracycline (tc), as widely used antibiotics, has been used for the various aspects of human lives, including mankind's medicine
Thing, veterinary drug etc..But because it has water solublity preferably, be difficult to be absorbed in metabolic process, great majority are by the shapes of urine and feces
Formula is discharged, thus easily becoming the class antibiotic storing in water environment and accumulating.Meanwhile, it to be also easily caused antibiotic resistance to
Property of medicine antibacterial (arb) and the generation of antibiotics resistance gene (arg), thus jeopardize health.Therefore, for protecting ecology ring
Border and human body health, the tetracycline effectively removing in water environment is very necessary.So far, remove tetracycline
Effectively method includes ion exchange, membrane filter method, photocatalytic degradation method and absorption method.Compared with additive method, due to inhaling
The economy of attached method, effectiveness and the feature of environmental protection and be widely used.
Shitosan is as a kind of nontoxic, biodegradable natural polymer, the quilt with its excellent absorption property
Extensively apply.But because it has poor mechanical performance and is difficult to separation from waste water after absorption and limits it actual
Application.Graphene oxide thin slice is product after chemical oxidation and stripping for the powdered graphite, after oxidation processes, graphite oxide
Alkene not only maintains the original excellent physical and chemical performance of graphite, and the many oxygen-containing group functional groups introducing, such as hydroxyl, carboxylic
Base, epoxy radicals etc., so that graphene oxide can widely be dispersed in water body and organic solvent, are easy to occur with other materials
Reaction.Therefore, graphene oxide and shitosan combination can not only be improved the mechanical performance of this composite, and suction can be improved
The ability of attached tetracycline.Due to fe3o4Granule has easily separated, hypotoxic feature, is applied in this composite, and can be
Separated in the presence of externally-applied magnetic field.And in order to prevent fe3o4It is decomposed in acid condition, we are by covering on its surface
One layer of sio of lid2, to ensure that it has more preferable stability.In a word, fe3o4@sio2- chitosan/oxidized Graphene magnetic core-shell
Nano composite material is the method by treating different things alike, under the crosslinked action of glutaraldehyde, by shitosan by fe3o4@sio2Nanometer
To in surface of graphene oxide, not only absorbability is improved this nano composite material particulate load, and is easy to reclaim
Using.
Content of the invention
The technical problem to be solved in the present invention is to overcome the deficiencies in the prior art, and exploitation one kind is prepared simple and segregative
Can be used for the magnetic core-shell nano composite material of adsorption treatment antibiotic waste water.
A kind of preparation method of magnetic core-shell nano composite material proposed by the present invention, is the method by treating different things alike,
Under the crosslinked action of glutaraldehyde, by shitosan by fe3o4@sio2Nano-particle loads in surface of graphene oxide, and should
Magnetic core-shell nanocomposite applications contain tetracycline wastewater in removal.
In technique scheme, described magnetic core-shell nano composite material is obtained by following steps:
(1) under magnetic stirring, the polystyrolsulfon acid-maleic acid sodium salt (pssma 3:1) taking 0.5～1g adds
Enter the stirring and dissolving in the beaker fill 10～20ml ethylene glycol solvent.It is subsequently added the fecl of 0.5～1g3·6h2O and 1～2g
Sodium acetate, stirring until being completely dissolved.Above-mentioned solution is transferred to 25～50ml and contains teflon-lined rustless steel
In high-pressure hydrothermal reaction kettle, reactor is placed in the baking oven being previously heated to 200 DEG C, reacting by heating 8～10h.Take out reaction
Kettle naturally cools to room temperature, isolates magnetic-particle with the method for Magneto separate or centrifugation, removes unreacted with secondary water washing
Reactant and by-product, 30～50 DEG C vacuum drying, prepare super-paramagnetic ferriferrous oxide nano granule.
(2) ferroso-ferric oxide of preparation in step (1) is scattered in standby in 6～12ml water.This is standby molten to take 1～2ml
Liquid is added in the mixed solution of 20～40ml ethanol, 1～2ml water and 1～2ml ammonia, and ultrasonic disperse is uniform.It is subsequently added
0.1～0.2ml tetraethyl orthosilicate (teos) and the mixed solution of 5～10ml ethanol, continue ultrasonic reaction 90min.Entered with Magnet
After row Magnetic Isolation, washing with alcohol obtains for three times by the ferroso-ferric oxide (fe of Silica-coated3o4@sio2) magnetic Nano
Granule.
(3) preparation process of graphene oxide is prepared with reference to hummers method.
(4), in take 2～4g shitosan to be dissolved in acetic acid solution that percentage by volume is 1～2%100ml, it is configured to quality hundred
Fraction is 2～4% chitosan solutions, and supersound process 30min.By magnetic fe in 0.5～1g step (2)3o4@sio2Magnetic
Nano-particle is added in this solution, stirs 1～2h.By in 50% glutaraldehyde solution of 10～15ml and 1～2g step (3)
Graphene oxide adds together to in three neck reaction flasks, adjusts ph=9～10, continues stirring 1～2h at 80 DEG C.To sink
Starch uses ethanol, distilled water wash successively, and is vacuum dried at 50～60 DEG C, that is, obtain final magnetic core-shell nano combined
Material.
In above-mentioned preparation method, the order of preparation is first to prepare fe3o4Nano-particle, then prepares fe again3o4@sio2Nanometer
Granule, then prepares graphene oxide with hummers method, and the method finally by treating different things alike, in the crosslinked action of glutaraldehyde
Under, by shitosan by fe3o4@sio2Nano-particle loads in surface of graphene oxide thus obtaining the said goods.
In above-mentioned preparation method, 200 DEG C of the maximum temperature in baking oven, and sustained response 8 hours under this temperature conditions.
In technique scheme, in described waste water, the concentration of tetracycline is preferably controlled in 0.01～0.5mmol/l (most preferably
For 0.02～0.4mmol/l).
In technique scheme, the ph value of described adsorption reaction is preferably 3～10 (most preferably 4～7).
In technique scheme, described sorption reaction time is preferably 0～24h.
Compared with prior art, it is an advantage of the current invention that:
1. the magnetic core-shell nano composite material of the present invention, main raw material(s) shitosan, graphite powder wide material sources, price is low
Honest and clean, it is easier to obtain, non-secondary pollution.The chemical drugss fecl using3·6h2O and teos etc. is conventional chemical products.
2. the preparation technology of magnetic core-shell nano composite material of the present invention and simple to operate, preparation is quick, the production cycle
Short, product recovery rate high it is not necessary to special chemical industry equipment, it is easy to accomplish industrialized production.
3. the magnetic core-shell nano composite material adsorption site of the present invention is many, and adsorption capacity is big, and tetracycline in waste water is gone
Removing solid capacity is higher.
4. the magnetic core-shell nano composite material of the present invention has magnetic, and reaction is easily isolated recovery, environment friend after terminating
Good, it is that the improvement of antibiotic pollution in waste water provides new approach.
Brief description
Fig. 1 is the scanning electron microscope schematic diagram of the magnetic core-shell nano composite material of the embodiment of the present invention 1；
Fig. 2 is the transmission electron microscope schematic diagram of the magnetic core-shell nano composite material of the embodiment of the present invention 1；
Fig. 3 is that in the embodiment of the present invention 1, the B-H loop of magnetic core-shell nano composite material divides under externally-applied magnetic field with it
From effect diagram.
Specific embodiment
Below with reference to Figure of description and specific embodiment, the present invention is described in further details.
Embodiment 1:
A kind of magnetic core-shell nano composite material of the present invention, the concrete preparation method of this composite is as follows:
(1) under magnetic stirring, the polystyrolsulfon acid-maleic acid sodium salt (pssma 3:1) taking 0.5g adds
The stirring and dissolving in the beaker fill 20ml ethylene glycol solvent.It is subsequently added the fecl of 0.54g3·6h2The sodium acetate of o and 1.5g,
Stirring is until being completely dissolved.Above-mentioned solution is transferred to 25ml and contains teflon-lined rustless steel high-pressure hydrothermal reaction kettle
In, reactor is placed in the baking oven being previously heated to 200 DEG C, reacting by heating 10h.Take out reactor and naturally cool to room temperature,
Isolate magnetic-particle with the method for Magneto separate or centrifugation, remove unreacted reactant and by-product with secondary water washing,
30 DEG C of vacuum drying, prepare super-paramagnetic ferriferrous oxide nano granule.
(2) ferroso-ferric oxide of preparation in step (1) is scattered in standby in 6ml water.This stock solution of 1ml is taken to be added to
In the mixed solution of 20ml ethanol, 1ml water and 1ml ammonia, ultrasonic disperse is uniform.It is subsequently added 0.1ml tetraethyl orthosilicate
(teos) and 5ml ethanol mixed solution, continue ultrasonic reaction 90min.Carried out with Magnet after Magnetic Isolation, washing with alcohol three times
Obtain by the ferroso-ferric oxide (fe of Silica-coated3o4@sio2) magnetic nanoparticle.
(3) preparation process of graphene oxide is prepared with reference to hummers method.
(4) 2g shitosan is taken to be dissolved in the acetic acid solution for 2%100ml for the percentage by volume, being configured to mass percent is
4% chitosan solution, and supersound process 30min.By magnetic fe in 0.75g step (2)3o4@sio2Magnetic nanoparticle adds
In this solution, stir 2h.50% glutaraldehyde solution of 15ml is added together with the graphene oxide in 1.5g step (3) to
To in three neck reaction flasks, adjust ph=9～10, continue stirring 1h at 80 DEG C.Precipitate is used successively ethanol, distillation washing
Wash, and be vacuum dried at 50 DEG C, that is, obtain final magnetic core-shell nano composite material.
Above-mentioned prepared magnetic core-shell nano composite material outward appearance is in brown color, is placed on and observes under scanning electron microscope, its
Surface texture is as shown in Figure 1 it can be seen that be dispersed with a large number by sio on graphene oxide layer surface2The fe of parcel3o4
(fe3o4@sio2) nano-particle.Material is observed under transmission electron microscope, as shown in Fig. 2 this nano-particle center is with fe3o4For
Core, sio2For shell, and by chitosan loaded in graphene oxide layer, fe is described3o4@sio2Nano-particle passes through shell and gathers
The interconnection function of sugar, is successfully supported in graphene oxide layer.Fig. 3 is the B-H loop of magnetic core-shell nano composite material
Figure, shows that magnetic core-shell nano composite material possesses good superparamagnetism, uses as adsorbent and can be good at reality
Existing solid-liquid separation and recycling.
Embodiment 2:
The magnetic core-shell nano composite material of the present invention processes the tetracycline in waste water, comprises the following steps:
Prepare the tetracycline that 8 parts of 50ml initial concentrations are 0.1mmol/l, adjusted with the hydrochloric acid or sodium hydroxide of 1mol/l
Section ph value is respectively 3,4,5,6,7,8,9,10.It is separately added into the magnetic core-shell nano composite material that 0.02g embodiment 1 is obtained,
It is placed in constant temperature water bath vibration case, keeping temperature is 25 DEG C, and rotating speed is 150 revs/min, with Magnet by composite wood after vibration 24h
Material separates from waste water, completes the process to tetracycline wastewater.Measured not to be adsorbed in waste water at 358nm with spectrophotometer
Fourth Ring cellulose content, the adsorbance of calculating the results are shown in Table 1.
Table 1: different ph values remove the impact of tetracycline in waste water to magnetic core-shell nano composite material
As shown in Table 1, different ph conditions are larger to Adsorption Effect.From 3～6, adsorbance is slowly increased ph, and is 6 in ph
When reach maximum, raise then as ph, adsorbance is gradually lowered.
Embodiment 3:
The magnetic core-shell nano composite material of the present invention processes the tetracycline in waste water, comprises the following steps:
Prepare the tetracycline that 10 parts of 50ml initial concentrations are 0.1mmol/l, with hydrochloric acid or the sodium hydroxide of 1mol/l
Adjusting ph is 6.Add the magnetic core-shell nano composite material adsorbent that above-described embodiment 1 is obtained, the consumption of this adsorbent is
0.02g.It is respectively placed in constant temperature water bath vibration case, keeping temperature is 25 DEG C, and rotating speed is 150 revs/min, and duration of oscillation is respectively
10,20,40,60,90,180,360,720,960,1440 minutes.After reaction terminates, with Magnet, composite is divided from waste water
From measuring Fourth Ring cellulose content not to be adsorbed in waste water at 358nm with spectrophotometer, the adsorbance of calculating the results are shown in Table 2.
Table 2: the adsorbance to tetracycline in waste water for the magnetic core-shell nano composite material in different time
As shown in Table 2, magnetic core-shell nano composite material increases continuous rising in time to the adsorbance of tetracycline in water,
After 360 minutes, tetracycline adsorbance tends towards stability, i.e. the time of equilibrium adsorption of magnetic core-shell nano composite material tetracycline adsorption
For 6h.
Embodiment 4:
The magnetic core-shell nano composite material of the present invention processes the tetracycline in waste water, comprises the following steps:
Respectively prepare 50ml concentration be 0.05,0.1,0.2,0.3, the tetracycline of 0.4mmol/l, with the salt of 1mol/l
Acid or sodium hydroxide adjust ph for 6.Add the magnetic core-shell nano composite material that above-described embodiment 1 is obtained, adsorbent amount
0.02g.It is respectively placed in constant temperature water bath vibration case, keeping temperature is 25 DEG C, and rotating speed is 150 revs/min, after vibration 24h, use magnetic
Composite is separated from waste water by ferrum, completes the process to tetracycline wastewater.Measure waste water with spectrophotometer at 358nm
In Fourth Ring cellulose content not to be adsorbed, the adsorbance of calculating the results are shown in Table 3.
Table 3: magnetic core-shell nano composite material contains the absorption of tetracycline wastewater to variable concentrations
As shown in Table 3, magnetic core-shell nano composite material is initial with tetracycline to the adsorbance of tetracycline in water
The increase of concentration constantly rises, and when tetracycline initial concentration is 0.05mmol/l, tetracycline adsorbance is 31.05mmol/
kg.During to 0.4mmol/l, the adsorbance of tetracycline reaches 139.29mmol/kg.
The above is only the preferred embodiment of the present invention, protection scope of the present invention is not limited merely to above-described embodiment,
With the various process programs of present inventive concept no substantial differences all in protection scope of the present invention.
Claims (7)
1. a kind of magnetic core-shell nano composite material is it is characterised in that described composite includes graphene oxide matrix, matrix
On be loaded with the fe that connects by shitosan3o4@sio2Nano-particle.
2. a kind of preparation method of magnetic core-shell nano composite material as claimed in claim 1, comprises the following steps:
(1) under magnetic stirring, the polystyrolsulfon acid-maleic acid sodium salt (pssma 3:1) taking 0.5～1g is added to
Fill stirring and dissolving in the beaker of 10～20ml ethylene glycol solvent.It is subsequently added the fecl of 0.5～1g3·6h2The second of o and 1～2g
Sour sodium, stirring is until being completely dissolved.Above-mentioned solution is transferred to 25～50ml and contains teflon-lined rustless steel high pressure
In hydrothermal reaction kettle, reactor is placed in the baking oven being previously heated to 200 DEG C, reacting by heating 8～10h.Take out reactor certainly
So it is cooled to room temperature, isolates magnetic-particle with the method for Magneto separate or centrifugation, removed with secondary water washing unreacted anti-
Answer thing and by-product, 30～50 DEG C of vacuum drying, prepare super-paramagnetic ferriferrous oxide nano granule.
(2) ferroso-ferric oxide of preparation in step (1) is scattered in standby in 6～12ml water.This stock solution of 1～2ml is taken to add
Enter in the mixed solution of 20～40ml ethanol, 1～2ml water and 1～2ml ammonia, ultrasonic disperse is uniform.It is subsequently added 0.1～
0.2ml tetraethyl orthosilicate (teos) and the mixed solution of 5～10ml ethanol, continue ultrasonic reaction 90min.Carry out magnetic with Magnet
After separating, washing with alcohol obtains for three times by the ferroso-ferric oxide (fe of Silica-coated3o4@sio2) magnetic nanoparticle.
(3) preparation process of graphene oxide is prepared with reference to hummers method.
(4), in take 2～4g shitosan to be dissolved in acetic acid solution that percentage by volume is 1～2%100ml, it is configured to mass percent
For 2～4% chitosan solutions, and supersound process 30min.By magnetic fe in 0.5～1g step (2)3o4@sio2Magnetic Nano
Granule is added in this solution, stirs 1～2h.By the oxidation in 50% glutaraldehyde solution of 10～15ml and 1～2g step (3)
Graphene adds together to in three neck reaction flasks, adjusts ph=9～10, continues stirring 1～2h at 80 DEG C.By precipitate
Use ethanol, distilled water wash successively, and be vacuum dried at 50～60 DEG C, that is, obtain the nano combined material of final magnetic core-shell
Material.
3. magnetic core-shell nano composite material according to claim 2 preparation method it is characterised in that preparation order
It is first to prepare fe3o4Nano-particle, then prepares fe again3o4@sio2Nano-particle, then uses hummers method preparation oxidation stone
Black alkene, the method finally by treating different things alike, under the crosslinked action of glutaraldehyde, by shitosan by fe3o4@sio2Nano-particle
Load in surface of graphene oxide thus obtaining the said goods.
4. a kind of purposes of magnetic core-shell nano composite material as claimed in claim 2 it is characterised in that: use described composite wood
Material removes the antibiotic in waste water.
5. utilization magnetic core-shell nano composite material according to claim 4 remove tetracycline in waste water it is characterised in that:
In described waste water, the concentration of tetracycline controls in 0.02～0.4mmol/l.
6. utilization magnetic core-shell nano composite material according to claim 4 remove tetracycline in waste water it is characterised in that:
The ph value of described adsorption reaction is 3～10.
7. utilization magnetic core-shell nano composite material according to claim 4 removes tetracycline in waste water, and described separation walks
Suddenly it is to be separated using Magnet.
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