CN106378093A - Preparation method and application of magnetic hollow graphene-based composite microsphere material - Google Patents
Preparation method and application of magnetic hollow graphene-based composite microsphere material Download PDFInfo
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- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/20—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising free carbon; comprising carbon obtained by carbonising processes
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- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28002—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their physical properties
- B01J20/28009—Magnetic properties
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- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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Abstract
The invention discloses a preparation method and application of a magnetic hollow graphene-based composite microsphere material. The preparation method comprises the following steps: taking a polymer microsphere with positive charges as a template, and obtaining the magnetic hollow graphene-based composite microsphere material through a high-temperature heat treatment one-step method. The preparation method provided by the invention is simple and feasible and has no environment pollution, and industrial production is easy to realize; meanwhile, the prepared magnetic hollow graphene-based composite microsphere material has a relatively large specific surface area and a developed pore structure, and can be used for efficiently and rapidly adsorbing and separating dye molecules. The magnetic hollow graphene-based composite microsphere material prepared by the preparation method has a wide application prospect in the aspect of treating dye wastewater.
Description
Technical field
The invention belongs to new carbon technical field is and in particular to a kind of graphene-based composite microsphere material of magnetic hollow
Preparation method and applications.
Background technology
With the high speed development of industrial technology, organic synthetic dye is in weaving, printing and dyeing, papermaking, printing, foods and cosmetics
It is widely applied in field, meanwhile, also produce substantial amounts of waste water from dyestuff.Waste water from dyestuff has that discharge capacity is big, colourity
Height, complicated component, chemical oxygen consumption (COC)（COD）Value is higher, the features such as toxicity is big.Substantial amounts of waste water from dyestuff discharge has had resulted in tight
The water pollution of weight and ecological disruption.For this reason, how effectively to administer the great attention that waste water from dyestuff causes people.
The method processing waste water from dyestuff at present mainly includes chemical method, bioanalysises, absorption method etc..Chemical method needs to water body
Middle interpolation chemical reagent, this easily causes secondary pollution, and is difficult to thoroughly eliminate dyestuff contaminant.The bioanalysises usual cycle is relatively
Long, technological process is complicated, and it is strict to run operation, and eliminate efficiency affected by water temperature, pH value etc. very big.Absorption method is because having technique
Simply, equipment investment is low, with low cost, non-environmental-pollution and the advantages of adsorption treatment effect is significant and receiving significant attention.
The key of impact adsorption efficiency is adsorbing material, therefore, develops inexpensive efficient adsorbing material most important.Porous carbon materials have
There are specific surface area height, pore structure prosperity, synthesis step is simple, economical and efficient, physicochemical properties are stable, good adsorption performance
The features such as, it is the first-selection of adsorbing material.The common active charcoal of material with carbon element adsorbent, mesoporous carbon, CNT and Graphene etc..
Graphene is a kind of new carbon of rising in recent years, is by sp2The two dimension of the carbon hexatomic ring composition of hydridization is single
The cycle honeycomb lattice structure of atomic layer, its thickness only has 0.335 nm.Compared with traditional material with carbon element, Graphene has many
Unique advantage, as high theoretical specific surface area（2600 m2/g）, prominent heat conductivility, good chemical stability and
Excellent mechanical property etc., presents good application prospect, for heavy metal ion, dyestuff in terms of substituting conventional adsorbent
Molecule, oil product etc. all have preferable absorption property.But because the particle diameter of Graphene is little, industrial traditional filtration and centrifugation handss
Duan Wufa is isolated recovery, and therefore, the Graphene after absorption pollutant is possible to bring serious secondary pollution.Additionally, by
Pi-pi bond between its adjacent sheets interacts, and Graphene easily occurs serious gathering or packing phenomenon, leads to its effective ratio table
Area reduces, thus reducing its absorbability.These problems seriously limit the practical application in adsorbing domain for the Graphene.
Give adsorbent magnetic, being separated efficiently and rapidly of adsorbent can be realized using magnetic separation technique.Therefore, develop
Magnetic graphene composite, for the separation efficiency improving graphene-based adsorbing material, reduces the secondary pollution after absorption and one-tenth
Originally have great importance.The preparation method of magnetic graphene composite mainly has chemical coprecipitation, hydro-thermal method, solvent thermal
Method and chemical reduction method.Take the magnetic graphene composite pattern of these methods preparation single, also relatively easy generation is poly-
Collection or packing phenomenon.The magnetic graphene composite reported at present is most of to be solid construction, and its specific surface area is relatively
Little, this have impact on the absorption property of magnetic graphene composite to a great extent.Inhale compared to the Graphene of solid construction
Enclosure material, the Graphene adsorbing material of hollow-core construction has that specific surface area is high, inner space is big, hole is abundant, heat stability good,
The low advantage of density, has important scientific research value and special application prospect in adsorbing domain.Wherein, high specific surface
Amass and create condition for the adsorbate in a large amount of " capture " solution, unique cavity structure and flourishing pore structure are adsorbate
Quick transmission provide passage, thus substantially increasing the adsorption efficiency to pollutant for the material.As can be seen here, construct hollow knot
Structure grapheme material is to reduce Graphene reunion degree, improve one of effective way of its absorption property.
Morphology controllable can be obtained, there is the hollow carbon sphere material of relatively high directionality using template, currently used
Hard mould agent mainly has SiO2Microsphere, polystyrene（PS）Microsphere, polymethyl methacrylate（PMMA）Microsphere etc..Using SiO2
When microsphere is template, one layer of polymeric is embedded on its surface by vapour deposition process or hydro-thermal method, then forms charcoal through carbonization again
Shell, finally removes silicon template with sodium hydroxide or Fluohydric acid., obtains hollow carbon sphere.This process synthesis step is more, and operation is relatively
Complexity, synthesis cycle is longer.Additionally, in preparation process, needing of can not avoiding is removed by sodium hydroxid or Fluohydric acid. etc.
Go template, this not only pollutes the environment, but also cost can be increased.During using PS or PMMA microsphere as template, can adopt
Specific solvent dissolving or high-temperature roasting go removing template to synthesize hollow carbon sphere.Yet with the PS being adopted or PMMA microsphere template
The surface of agent generally all assumes inertia, leads to Graphene easily to be reunited, and the hollow-core construction Graphene microsphere synthesizing exists controlled
Property is poor, bad dispersibility, absorption property are low and the problems such as difficult separation and recycling.Therefore, develop one kind practicable hollow
The efficient preparation technology of structure graphite alkene microsphere has very important theory value and practical significance.
Content of the invention
For deficiencies of the prior art, the present invention provides a kind of graphene-based composite microsphere material of magnetic hollow
Preparation method and applications it is intended to solve produce at present hollow-core construction Graphene micro-sphere material preparation process poor controllability,
The absorption property of bad dispersibility and product is low, reclaim the technical problems such as separation difficulty.
To achieve these goals, the technical solution used in the present invention is as follows：A kind of magnetic hollow is graphene-based compound micro-
The preparation method of ball material, by from suitable template and self assembly strategy, being realized by high-temperature heat treatment one-step method
The controllable standby of magnetic hollow structure graphite thiazolinyl composite microsphere material, its preparating mechanism schematic diagram is as shown in Figure 1.First, will
The positively charged polymer microballoon dispersion liquid in surface is added to the negatively charged graphene oxide in surface（GO-）In dispersion liquid, lead to
Cross the polymer microballoon that electrostatic self-assembled forms graphene oxide parcel, mixed dispersion liquid obtained above adds gold in right amount
Belong to saline solution, positively charged metal ion is fully adsorbed by electrostatic interaction（Mx+）, pass through high-temperature heat treatment one afterwards
Footwork removes polymer microballoon template, and meanwhile, the metal ion of absorption changes into magnetic nano-particle, graphene oxide composition
Also it is reduced into Graphene, thus obtaining the graphene-based composite microsphere material of magnetic hollow.
Specifically include following steps：
S1：Polymer microballoon dispersion liquid is added in graphene oxide dispersion, magnetic agitation 2 ~ 5h, obtains mixing dispersion
Liquid.
S2：Add slaine in the mixed dispersion liquid obtaining to step S1, and continue magnetic agitation 12 ~ 24h, be filtrated to get
Solid product；After scrubbed for this solid product and dry, it is placed in protective gas atmosphere, is heated to 500 ~ 900 DEG C, carry out height
Warm roasting 2 ~ 5h；Then naturally cool to room temperature, obtain final product the graphene-based composite microsphere material of magnetic hollow.
In step sl, the mass ratio of the graphene oxide in mixed dispersion liquid and polymer microballoon is 1：（5~15）, should
Ratio is so that graphene oxide is completely effectively coated to polymer microballoon.
The mass ratio of the graphene oxide in the slaine adding in step s 2 and mixed dispersion liquid is（1~30）：1；Should
It is dispersed in Graphene that ratio is beneficial to gained magnetic metal material in product, and graphite olefinic substance do not occur stacking or
Clustering phenomena.Described slaine is the salt containing ferrum, cobalt, nickel or manganese.
The concentration of the graphene oxide dispersion described in step S1 is 1 ~ 10mg/mL, and prepares graphene oxide and can adopt
With improved Hummers method, preparation process is：
a：Under the conditions of ice-water bath, the concentrated sulphuric acid of mass fraction 95 ~ 98% is added in sodium nitrate and the mixture of graphite powder, stirs
Mix reaction 10 ~ 60min；
b：Add potassium permanganate, continue reaction 12 ~ 48h, keeping temperature≤20 DEG C in course of reaction；
c：Add the deionized water as diluent stirring reaction 30min, obtain reaction solution；It is warming up to 98 DEG C and be incubated
48h, the color of question response solution becomes brown color from black；
d：To in the reaction solution of above-mentioned brown color, Deca mass fraction is 35% hydrogen peroxide so as to continue to react 30min, makes
The reaction solution of brown color becomes jonquilleous reaction solution；
e：Filter above-mentioned jonquilleous reaction solution, then be 5 ~ 10% HCl solution and deionized water wash filtration with mass fraction
The solid matter obtaining, is dried to constant weight at room temperature, obtains final product graphene oxide；
f：At room temperature, add graphene oxide in deionized water, after ultrasonic agitation, form graphene oxide dispersion.
Wherein：Described graphite powder, sodium nitrate, concentrated sulphuric acid, the ratio of the consumption of potassium permanganate, diluent and hydrogen peroxide are
（0.5~5.5g）：（0.5~5.5g）：（90~300ml）：（5~25g）：（25~350ml）：（50~100ml）, this ratio is beneficial to obtain
Specific surface area is big, size and the moderate graphene oxide product of the number of plies.
Polymer microballoon dispersion liquid described in step S1 is the positively charged poly- methyl-prop in surface that concentration is 1 ~ 15wt%
E pioic acid methyl ester（PMMA）Microsphere dispersion liquid, from positively charged radical initiator azo diisobutyl amidine hydrochlorate
（AMPMDHC）Methyl Methacrylate（MMA）Monomer is polymerized, and carries positive charge by surfactant- free emulsion polymerization synthetic surface
Monodispersity PMMA microsphere, its preparation process is：MMA is mixed to get MMA solution with water, stirs under protective gas atmosphere
30~60min；Again reaction temperature is increased between 50 ~ 70 DEG C, adds AMPMDHC and water, be polymerized anti-at a temperature of 60 ~ 80 DEG C
Answer 1 ~ 6h, that is, obtain the PMMA microsphere dispersion liquid of surface band positive charge；The mass ratio of wherein MMA and AMPMDHC is 1：（0.001~
0.002）.
Polymer microballoon dispersion liquid described in step S1 can also be positively charged the gathering in surface that concentration is 1 ~ 15wt%
Styrene（PS）Microsphere dispersion liquid, its preparation process is：
（1）Styrene, Polyvinylpyrrolidone, 2,2 '-azo diisobutyl amidine dihydrochloride and water are pressed the ratio of consumption（6~
10g）：（1~1.5g）：（0.2~0.3g）：（100~200ml）It is added sequentially in reaction vessel, and stir under protective gas atmosphere
Mix 30 ~ 60min, then heat between 50 ~ 80 DEG C, be allowed to carry out polyreaction 12 ~ 48h；
（2）Use ethanol and deionized water centrifugation, cleaning successively, filter, obtain the PS microsphere that surface carries positive charge；With water it is again
Solvent, is configured to PS microsphere dispersion liquid.
The protective gas being related in above-mentioned steps is usually nitrogen or argon.
The heating rate of high-temperature calcination process is 0.5 ~ 10 DEG C/min, and the flow velocity of protective gas is 50-150mL/min.Institute
Selected heating rate is beneficial to the shielding gas that high-temperature heat treatment process high temperature cracking reaction carries out fully and completely, being selected
Rate of flow of fluid generates hollow-core construction and microcellular structure of product etc. after being beneficial to protect Pintsch process.
The graphene-based complex microsphere of magnetic hollow prepared by the present invention has up to 900 ~ 2000m2The specific surface area of/g,
Total pore volume is 0.35 ~ 0.6cm3/ g, Micropore volume is 0.22 ~ 0.4cm3/g.
Application in dye wastewater treatment for the graphene-based composite microsphere material of magnetic hollow prepared using said method.
The graphene-based composite microsphere material of magnetic hollow prepared by the present invention is for acid blue 92, orange beta-naphthol, malachite green oxalate, rhodamine
The dye molecule such as B and methylene blue has good absorption property.
Compared with prior art, the present invention has the advantages that：
1st, the Graphene microsphere of present invention preparation is hollow-core construction, and specific surface area is big.The Graphene microsphere of report is most of at present
For solid construction, the Graphene micro-sphere material prepared by the present invention is hollow-core construction, can increase Graphene to greatest extent
Specific surface area, and then increase its saturated extent of adsorption；Unique cavity structure and flourishing pore structure are the quick biography of adsorbate
Defeated provide passage, thus increasing substantially the adsorption efficiency to pollutant for the material.
2nd, good dispersion, controllability is strong.The polymer microballoon template such as the PS microsphere in the past adopting or PMMA microsphere is usual
It is surface inactive, lead to synthesized hollow-core construction Graphene microsphere to there is poor controllability, bad dispersibility and separation and recovery tired
Difficult the shortcomings of.It is template that the present invention adopts the positively charged PS microsphere in surface or PMMA microsphere, by its surface self-organization
Negatively charged graphene oxide it is ensured that in dispersion liquid each component be uniformly dispersed, this self assembly strategy can be prevented effectively from graphite
The gathering of alkene or packing phenomenon, gained hollow-core construction Graphene microsphere has homogeneous size and morphology controllable, and well
Monodispersity.
3rd, synthetic method environmental protection, efficiently.The formation of magnetic nano-particle in the present invention, graphene oxide composition reduction with
And the removal of template is by the realization of high-temperature heat treatment method one step, it is to avoid using the virose reducing agent of tool（As hydrazine hydrate, boron hydrogen
Change sodium etc.）Graphene is reduced, there is high efficiency, low cost, green safety.
4th, advantages of good adsorption effect.The oxygen-containing functional group of polymer microballoon template of the present invention and graphene oxide exists
Substantial amounts of gas is produced so that gained Graphene composite microsphere material has abundant three-dimensional porous skeleton in pyrolysis process
Structure, giving products therefrom high specific surface area, increased adsorption site, thus improve the suction of Graphene composite microsphere material
Attached speed and adsorbance.
5th, facilitate desorption, be easy to reclaim.The graphene-based complex microsphere of magnetic hollow of gained of the present invention has distinctive
Magnetic responsiveness, can carry out efficient sharp separation by externally-applied magnetic field it is not necessary to the operation such as traditional filtration and centrifugation, no secondary
Pollution, enormously simplify the technological process of preparation, effectively reduces preparation cost, and solving the difficult detached reality of adsorbing material should
Use problem.The graphene-based composite microsphere material of gained magnetic hollow of the present invention has that absorption property is strong, easily separated recovery, no secondary
The advantages of pollution.
6th, low cost, easily promotes.Preparation method of the present invention is simple, processing ease, low cost, and is easy to carry out on a large scale
Produce.
Brief description
Fig. 1 is the preparating mechanism schematic diagram of the graphene-based composite microsphere material of magnetic hollow；
The scanning electron microscope (SEM) photograph of the positively charged PMMA microsphere in surface prepared by embodiment one for the Fig. 2；
Fig. 3 is the PMMA prepared by embodiment one+/GO-The scanning electron microscope (SEM) photograph of complex microsphere；
Fig. 4 is the scanning electron microscope (SEM) photograph of the graphene-based complex microsphere of magnetic hollow prepared by embodiment one.
Specific embodiment
With reference to specific embodiment, the present invention is described in further detail.
Embodiment one
Prepare the graphene-based composite microsphere material of magnetic hollow in the following ways, and it is real to apply this micro-sphere material to carry out absorption
Test.
1st, the preparation of graphene oxide
Graphene oxide is prepared using improved Hummers method, its technological process is as follows：Reaction is assembled in ice-water bath
Device, adds 1g expanded graphite powder and 2.5g sodium nitrate, adding 150ml mass percent is under agitation in reaction bulb
95% concentrated sulphuric acid, reacts 30min in ice-water bath；Subsequently, add 15g potassium permanganate, controlling reaction temperature is less than 20 DEG C,
Continue reaction 12h；Add 150ml deionized water to be diluted, after stirring reaction 30min, be warming up to 98 DEG C, be incubated 48h, molten
Liquid color becomes brown color from black transitions, obtains the crude product of graphene oxide.To in above-mentioned crude product, Deca 50ml mass is divided
The oxidant of the hydrogen peroxide reduction residual for 35% for the number, continues reaction 30min, solution becomes glassy yellow after dripping off；Filter, wash
With obtain graphite oxide ene product after drying.With water as solvent, graphene oxide is configured to the GO dispersion liquid of 2mg/ml.
2nd, the positively charged polymethyl methacrylate in surface（PMMA）The preparation of microsphere template
From positively charged radical initiator azo diisobutyl amidine hydrochlorate（AMPMDHC）Methyl Methacrylate
（MMA）Monomer is polymerized, and carries the monodispersity PMMA microsphere of positive charge by surfactant- free emulsion polymerization synthetic surface.Concrete technology
Flow process is：10g MMA and 165ml water are added in the reactor of 250ml, under nitrogen gas protection, stir 30min, will be anti-
Answer temperature to be increased to 70 DEG C, add 0.015g AMPMDHC and 5ml water, polyreaction 6h at a temperature of 70 DEG C, obtaining concentration is
The positively charged PMMA microsphere dispersion liquid in the surface of 10wt%.The scanning electron microscope (SEM) photograph of gained PMMA microsphere is as shown in Fig. 2 from figure
It can be seen that the particle diameter of PMMA microsphere material is highly uniform, mean diameter is about 200 nm, has good monodispersity, does not have
Occur assembling or packing phenomenon.
3rd, the preparation of the graphene-based composite microsphere material of magnetic hollow
PMMA microsphere dispersion liquid positively charged for the surface of 10wt% is added in 2mg/ml graphene oxide dispersion, magnetic force
Stirring 2h, makes PMMA microsphere and graphene oxide be self-assembled into uniform dispersion liquid by electrostatic interaction, obtains PMMA+/
GO-Complex microsphere, is subsequently adding the FeSO of 2.5mmol4· 7H2O solution, continues magnetic agitation 20h, will produce after filtration drying
Thing 700 DEG C of calcining 3h in inert gas atmosphere, obtain the graphene-based composite microsphere material of magnetic hollow after being cooled to room temperature.Its
In, PMMA prepared by this embodiment+/GO-The scanning electron microscope (SEM) photograph of complex microsphere is as shown in figure 3, as can be seen from the figure in microsphere
Surface is closely coated with film like material, shows that graphite oxide olefinic constituent is successfully assembled in the surface of PMMA microsphere, PMMA+/GO-
Complex microsphere also has good monodispersity, does not occur assembling or packing phenomenon in self assembling process.Gained magnetic is empty
The scanning electron microscope (SEM) photograph of cardiolith mertenyl composite microsphere material as shown in figure 4, as can be seen from the figure composite microsphere material there are rule
Three-dimensional macroporous structure then, size is about 200 nm, removes, mainly due to high-temperature calcination process, three producing after PMMA template
Dimension macroporous structure.
4th, the absorption to dye molecule for the graphene-based composite microsphere material of magnetic hollow
The specific surface area of the graphene-based composite microsphere material of the magnetic hollow prepared by the present embodiment is 987m2/ g, total pore volume is
0.56cm3/ g, Micropore volume is 0.36cm3/ g, has good absorption property for dye molecule.After absorbing dye, adsorbent
Externally-applied magnetic field sharp separation can be passed through.The graphene-based complex microsphere of magnetic hollow that table 1 is prepared in the present embodiment is to dye
The absorption property situation of material molecule, as can be seen from the table, the graphene-based complex microsphere of prepared magnetic hollow divides to dyestuff
Son has efficient adsorption effect, and adsorbent has magnetic, it is possible to achieve efficiently rapid magnetic separates, it is to avoid secondary dirt
Dye, shows that its renewable performance is good, to acid blue 92, orange beta-naphthol, malachite green oxalate, rhodamine B and methylene after circulating 10 times
Blue clearance is all more than 75%.
The absorption property to dye molecule for the graphene-based composite microsphere material of magnetic hollow prepared by table 1 embodiment 1
| Cycle-index | Acid blue 92 clearance（%） | Orange beta-naphthol clearance（%） | Malachite green oxalate clearance（%） | Rhodamine B clearance（%） | Methylene blue clearance（%） |
| 1 | 99 | 99 | 99 | 99 | 98 |
| 2 | 98 | 98 | 98 | 98 | 97 |
| 3 | 97 | 97 | 97 | 97 | 96 |
| 4 | 96 | 96 | 96 | 96 | 95 |
| 5 | 95 | 95 | 95 | 95 | 94 |
| 6 | 93 | 93 | 94 | 92 | 91 |
| 7 | 91 | 91 | 92 | 89 | 88 |
| 8 | 88 | 88 | 88 | 87 | 86 |
| 9 | 85 | 84 | 84 | 83 | 82 |
| 10 | 80 | 79 | 79 | 76 | 75 |
Embodiment two
Prepare the graphene-based composite microsphere material of magnetic hollow in the following ways, and it is real to apply this micro-sphere material to carry out absorption
Test.
1st, the preparation of graphene oxide
Graphene oxide is prepared using improved Hummers method, its technological process is as follows：Reaction is assembled in ice-water bath
Device, adds 1g expanded graphite powder and 2.5g sodium nitrate, adding 150ml mass percent is under agitation in reaction bulb
98% concentrated sulphuric acid, reacts 60min in ice-water bath；Subsequently, add 15g potassium permanganate, controlling reaction temperature is less than 20 DEG C,
Continue reaction 24h；Add 150ml deionized water to be diluted, after stirring reaction 30min, be warming up to 98 DEG C, be incubated 48h, molten
Liquid color becomes brown color from black transitions, obtains the crude product of graphene oxide.To in above-mentioned crude product, Deca 50ml mass is divided
The oxidant of the hydrogen peroxide reduction residual for 35% for the number, continues reaction 30min, solution becomes glassy yellow after dripping off；Filter, wash
With obtain graphite oxide ene product after drying.With water as solvent, graphene oxide is configured to the GO dispersion liquid of 1mg/ml.
2nd, the positively charged polystyrene in surface（PS）The preparation of microsphere template agent
By 8g styrene, 1.2g Polyvinylpyrrolidone, 2,2 '-azo diisobutyl amidine dihydrochloride of 0.25g and 150mL water
It is added sequentially in reaction vessel, be stirred 60min under nitrogen gas protection, be warming up to 70 DEG C, be incubated polyreaction
24h, uses ethanol and deionized water centrifugation, cleaning successively, filters, obtain the PS microsphere that surface carries positive charge.With water as solvent,
Gained PS microsphere is made into the PS microsphere dispersion liquid that concentration is 10wt%.
3rd, the preparation of the graphene-based composite microsphere material of magnetic hollow
PS microsphere dispersion liquid positively charged for the surface of 8wt% is added in 1mg/ml graphene oxide dispersion, magnetic agitation
2h, makes PS microsphere and graphene oxide be self-assembled into uniform dispersion liquid by electrostatic interaction, is subsequently adding 0.56g's
FeSO4· 7H2O solution, continues magnetic agitation 20h, after filtration drying, 750 DEG C product is calcined 3h in inert gas atmosphere,
The graphene-based complex microsphere of magnetic hollow is obtained after being cooled to room temperature.
（4）The absorption to dye molecule for the graphene-based composite microsphere material of magnetic hollow
The specific surface area of the graphene-based composite microsphere material of the magnetic hollow prepared by the present embodiment is 992m2/ g, total pore volume is
0.55cm3/ g, Micropore volume is 0.34cm3/ g, has good absorption property for dye molecule.After absorbing dye, adsorbent
Externally-applied magnetic field sharp separation can be passed through.The graphene-based complex microsphere of magnetic hollow that table 2 is prepared in the present embodiment is to dye
The absorption property situation of material molecule, as can be seen from the table, the graphene-based complex microsphere of prepared magnetic hollow divides to dyestuff
Son has efficient adsorption effect, and adsorbent has magnetic and can realize efficient rapid magnetic and separates, it is to avoid secondary pollution,
Show that its renewable performance is good, to acid blue 92, orange beta-naphthol, malachite green oxalate, rhodamine B and methylene blue after circulating 10 times
Clearance is all more than 75%.
The absorption property to dye molecule for the graphene-based composite microsphere material of magnetic hollow prepared by table 2 embodiment 2
| Cycle-index | Acid blue 92 clearance（%） | Orange beta-naphthol clearance（%） | Malachite green oxalate clearance（%） | Rhodamine B clearance（%） | Methylene blue clearance（%） |
| 1 | 99 | 99 | 99 | 98 | 97 |
| 2 | 98 | 98 | 98 | 97 | 96 |
| 3 | 97 | 98 | 98 | 97 | 95 |
| 4 | 95 | 95 | 96 | 96 | 93 |
| 5 | 93 | 94 | 94 | 93 | 92 |
| 6 | 90 | 91 | 92 | 89 | 88 |
| 7 | 87 | 86 | 87 | 86 | 85 |
| 8 | 84 | 83 | 84 | 83 | 82 |
| 9 | 81 | 79 | 78 | 78 | 77 |
| 10 | 77 | 75 | 75 | 75 | 75 |
Embodiment three
Prepare the graphene-based composite microsphere material of magnetic hollow in the following ways, and it is real to apply this micro-sphere material to carry out absorption
Test.
1st, the preparation of graphene oxide
Graphene oxide is prepared using improved Hummers method, its technological process is as follows：Reaction is assembled in ice-water bath
Device, adds 1g expanded graphite powder and 2.5g sodium nitrate, adding 150ml mass percent is under agitation in reaction bulb
98% concentrated sulphuric acid, reacts 60min in ice-water bath；Subsequently, add 15g potassium permanganate, controlling reaction temperature is less than 20 DEG C,
Continue reaction 36h；Add 150ml deionized water to be diluted, after stirring reaction 30min, be warming up to 98 DEG C, be incubated 48h, molten
Liquid color becomes brown color from black transitions, obtains the crude product of graphene oxide.To in above-mentioned crude product, Deca 50ml mass is divided
The oxidant of the hydrogen peroxide reduction residual for 35% for the number, continues reaction 30min, solution becomes glassy yellow after dripping off；Filter, wash
With obtain graphite oxide ene product after drying.With water as solvent, graphene oxide is configured to the GO dispersion liquid of 2mg/ml.
2nd, the preparation of the positively charged PMMA microsphere template in surface
Cause the polymerization of MMA monomer from positively charged radical initiator AMPMDHC, table is synthesized by surfactant- free emulsion polymerization
Face carries the monodispersity PMMA microsphere of positive charge.Concrete technology flow process is：10g MMA and 115ml water are added to 250ml's
In reactor, nitrogen gas protection under stir 60min, reaction temperature is increased to 70 DEG C, add 0.015g AMPMDHC and
5ml water, polyreaction 3h at a temperature of 70 DEG C, obtain the positively charged PMMA microsphere dispersion liquid in the surface for 15wt% for the concentration.
3rd, the preparation of the graphene-based composite microsphere material of magnetic hollow
PMMA microsphere dispersion liquid positively charged for the surface of 15wt% is added in 1mg/ml graphene oxide dispersion, magnetic force
Stirring 3h, makes PMMA microsphere and graphene oxide be self-assembled into uniform dispersion liquid by electrostatic interaction, is subsequently adding
The FeCl of 0.27g3· 6H2O solution, continues magnetic agitation 18h, after filtration drying by product 800 DEG C in inert gas atmosphere
Calcining 2.5h, obtains the graphene-based complex microsphere of magnetic hollow after being cooled to room temperature.
4th, the absorption to dye molecule for the graphene-based composite microsphere material of magnetic hollow
The specific surface area of the graphene-based composite microsphere material of the magnetic hollow prepared by the present embodiment is 942m2/ g, total pore volume is
0.52cm3/ g, Micropore volume is 0.29cm3/ g, has good absorption property for dye molecule.After absorbing dye, adsorbent
Externally-applied magnetic field sharp separation can be passed through.The graphene-based complex microsphere of magnetic hollow that table 3 is prepared in the present embodiment is to dye
The absorption property situation of material molecule, as can be seen from the table, the graphene-based complex microsphere of prepared magnetic hollow divides to dyestuff
Son has efficient adsorption effect, and adsorbent has magnetic, it is possible to achieve efficiently rapid magnetic separates, it is to avoid secondary dirt
Dye, shows that its renewable performance is good, to acid blue 92, orange beta-naphthol, malachite green oxalate, rhodamine B and methylene after circulating 10 times
Blue clearance is all more than 75%.
The absorption property to dye molecule for the graphene-based composite microsphere material of magnetic hollow prepared by table 3 embodiment 3
| Cycle-index | Acid blue 92 clearance（%） | Orange beta-naphthol clearance（%） | Malachite green oxalate clearance（%） | Rhodamine B clearance（%） | Methylene blue clearance（%） |
| 1 | 99 | 99 | 99 | 99 | 98 |
| 2 | 98 | 98 | 98 | 98 | 98 |
| 3 | 97 | 97 | 97 | 97 | 97 |
| 4 | 95 | 95 | 96 | 95 | 96 |
| 5 | 94 | 94 | 95 | 94 | 95 |
| 6 | 92 | 92 | 93 | 92 | 93 |
| 7 | 90 | 90 | 91 | 90 | 90 |
| 8 | 88 | 88 | 88 | 88 | 87 |
| 9 | 85 | 84 | 84 | 84 | 84 |
| 10 | 81 | 80 | 81 | 77 | 76 |
Example IV
Prepare the graphene-based composite microsphere material of magnetic hollow in the following ways, and it is real to apply this micro-sphere material to carry out absorption
Test.
1st, the preparation of graphene oxide
Graphene oxide is prepared using improved Hummers method, its technological process is as follows：Reaction is assembled in ice-water bath
Device, adds 1g expanded graphite powder and 2.5g sodium nitrate, adding 150ml mass percent is under agitation in reaction bulb
95% concentrated sulphuric acid, reacts 40min in ice-water bath；Subsequently, add 15g potassium permanganate, controlling reaction temperature is less than 20 DEG C,
Continue reaction 48h；Add 150ml deionized water to be diluted, after stirring reaction 30min, be warming up to 98 DEG C, be incubated 48h, molten
Liquid color becomes brown color from black transitions, obtains the crude product of graphene oxide.To in above-mentioned crude product, Deca 50ml mass is divided
The oxidant of the hydrogen peroxide reduction residual for 35% for the number, continues reaction 30min, solution becomes glassy yellow after dripping off；Filter, wash
With obtain graphite oxide ene product after drying.With water as solvent, graphene oxide is configured to the GO dispersion liquid of 1mg/ml.
2nd, the preparation of the positively charged PS microsphere template agent in surface
By 10g styrene, 1.5g Polyvinylpyrrolidone, 2,2 '-azo diisobutyl amidine dihydrochloride of 0.3g and 180mL water
It is added sequentially in reaction vessel, be stirred 60min under nitrogen gas protection, be warming up to 65 DEG C, be incubated polyreaction
48h, uses ethanol and deionized water centrifugation, cleaning successively, filters, obtain the PS microsphere that surface carries positive charge.With water as solvent,
Gained PS microsphere is made into the PS microsphere dispersion liquid that concentration is 15wt%.
3rd, the preparation of the graphene-based composite microsphere material of magnetic hollow
PS microsphere dispersion liquid positively charged for the surface of 15wt% is added in 1mg/ml graphene oxide dispersion, magnetic force stirs
Mix 2h, make PS microsphere and graphene oxide be self-assembled into uniform dispersion liquid by electrostatic interaction, be subsequently adding 0.2g's
FeCl3· 6H2O solution, continues magnetic agitation 20h, after filtration drying, 750 DEG C product is calcined 3h in inert gas atmosphere,
The graphene-based complex microsphere of magnetic hollow is obtained after being cooled to room temperature.
4th, the absorption to dye molecule for the graphene-based composite microsphere material of magnetic hollow
The specific surface area of the graphene-based composite microsphere material of the magnetic hollow prepared by the present embodiment is 915m2/ g, total pore volume is
0.55cm3/ g, Micropore volume is 0.31cm3/ g, has good absorption property for dye molecule.After absorbing dye, adsorbent
Externally-applied magnetic field sharp separation can be passed through.The graphene-based complex microsphere of magnetic hollow that table 4 is prepared in the present embodiment is to dye
The absorption property situation of material molecule, as can be seen from the table, the graphene-based complex microsphere of prepared magnetic hollow divides to dyestuff
Son has efficient adsorption effect, and adsorbent has magnetic, it is possible to achieve efficiently rapid magnetic separates, it is to avoid secondary dirt
Dye, shows that its renewable performance is good, to acid blue 92, orange beta-naphthol, malachite green oxalate, rhodamine B and methylene after circulating 10 times
Blue clearance is all more than 70%.
The absorption property to dye molecule for the graphene-based composite microsphere material of magnetic hollow prepared by table 4 embodiment 4
| Cycle-index | Acid blue 92 clearance（%） | Orange beta-naphthol clearance（%） | Malachite green oxalate clearance（%） | Rhodamine B clearance（%） | Methylene blue clearance（%） |
| 1 | 99 | 99 | 99 | 99 | 98 |
| 2 | 98 | 98 | 98 | 98 | 97 |
| 3 | 97 | 97 | 97 | 97 | 96 |
| 4 | 95 | 95 | 96 | 95 | 94 |
| 5 | 93 | 93 | 94 | 93 | 92 |
| 6 | 90 | 90 | 91 | 90 | 89 |
| 7 | 86 | 86 | 88 | 86 | 85 |
| 8 | 83 | 83 | 85 | 82 | 81 |
| 9 | 81 | 80 | 81 | 78 | 77 |
| 10 | 77 | 76 | 77 | 74 | 73 |
The above embodiment of the present invention only example to illustrate the invention, and be not to embodiments of the present invention
Restriction.For those of ordinary skill in the field, other not similar shapes can also be made on the basis of the above description
The change of formula and variation.Here all of embodiment cannot be exhaustive.Every technical scheme that belongs to is drawn
Obvious change that Shen goes out or change the row still in protection scope of the present invention.
Claims (10)
1. a kind of preparation method of the graphene-based composite microsphere material of magnetic hollow is it is characterised in that comprise the following steps：
S1：Polymer microballoon dispersion liquid is added in graphene oxide dispersion, magnetic agitation 2 ~ 5h, obtains mixing dispersion
Liquid；
S2：Add slaine in the mixed dispersion liquid obtaining to step S1, and continue magnetic agitation 12 ~ 24h, be filtrated to get solid-state
Product；After scrubbed for this solid product and dry, it is placed in protective gas atmosphere, is heated to 500 ~ 900 DEG C, carry out high temperature roasting
Burn 2 ~ 5h；Then naturally cool to room temperature, obtain final product the graphene-based composite microsphere material of magnetic hollow.
2. the graphene-based composite microsphere material of magnetic hollow according to claim 1 preparation method it is characterised in that
In step S1, the graphene oxide in mixed dispersion liquid and the mass ratio of polymer microballoon are 1：（5~15）.
3. the graphene-based composite microsphere material of magnetic hollow according to claim 1 preparation method it is characterised in that
The mass ratio of the graphene oxide in the slaine and the mixed dispersion liquid that add in step S2 is（1~30）：1；Described slaine
It is the salt containing ferrum, cobalt, nickel or manganese.
4. the preparation method of the graphene-based composite microsphere material of magnetic hollow according to claim 1 is it is characterised in that step
The concentration of the graphene oxide dispersion described in rapid S1 is 1 ~ 10mg/mL, and its preparation process is：
a：Under the conditions of ice-water bath, the concentrated sulphuric acid of mass fraction 95 ~ 98% is added in sodium nitrate and the mixture of graphite powder, stirs
Mix reaction 10 ~ 60min；
b：Add potassium permanganate, continue reaction 12 ~ 48h, keeping temperature≤20 DEG C in course of reaction；
c：Add the deionized water as diluent stirring reaction 30min, obtain reaction solution；It is warming up to 98 DEG C and be incubated
48h, the color of question response solution becomes brown color from black；
d：To in the reaction solution of above-mentioned brown color, Deca mass fraction is 35% hydrogen peroxide so as to continue to react 30min, makes
The reaction solution of brown color becomes jonquilleous reaction solution；
e：Filter above-mentioned jonquilleous reaction solution, then be 5 ~ 10% HCl solution and deionized water wash filtration with mass fraction
The solid matter obtaining, is dried to constant weight at room temperature, obtains final product graphene oxide；
f：At room temperature, add graphene oxide in deionized water, after ultrasonic agitation, form graphene oxide dispersion.
5. the preparation method of the graphene-based composite microsphere material of magnetic hollow according to claim 4 is it is characterised in that institute
The ratio of the consumption of graphite powder, sodium nitrate, concentrated sulphuric acid, potassium permanganate, diluent and hydrogen peroxide stated is（0.5~5.5g）：（0.5~
5.5g）：（90~300ml）：（5~25g）：（25~350ml）：（50~100ml）.
6. the preparation method of the graphene-based composite microsphere material of magnetic hollow according to claim 1 is it is characterised in that step
Polymer microballoon dispersion liquid described in rapid S1 is the positively charged PMMA microsphere dispersion liquid in surface that concentration is 1 ~ 15wt%, its
Preparation process is：
MMA is mixed to get MMA solution with water, stirs 30 ~ 60min under protective gas atmosphere；Again reaction temperature is increased to
Between 50 ~ 70 DEG C, add AMPMDHC and water, polyreaction 1 ~ 6h at a temperature of 60 ~ 80 DEG C, that is, obtain surface band positive charge
PMMA microsphere dispersion liquid；The mass ratio of wherein MMA and AMPMDHC is 1：（0.001~0.002）.
7. the preparation method of the graphene-based composite microsphere material of magnetic hollow according to claim 1 is it is characterised in that step
Polymer microballoon dispersion liquid described in rapid S1 is the positively charged PS microsphere dispersion liquid in surface that concentration is 1 ~ 15wt%, its system
For step it is：
（1）Styrene, Polyvinylpyrrolidone, 2,2 '-azo diisobutyl amidine dihydrochloride and water are pressed the ratio of consumption（6~
10g）：（1~1.5g）：（0.2~0.3g）：（100~200ml）It is added sequentially in reaction vessel, and stir under protective gas atmosphere
Mix 30 ~ 60min, then heat between 50 ~ 80 DEG C, be allowed to carry out polyreaction 12 ~ 48h；
（2）Use ethanol and deionized water centrifugation, cleaning successively, filter, obtain the PS microsphere that surface carries positive charge；With water it is again
Solvent, is configured to PS microsphere dispersion liquid.
8. the preparation method of the graphene-based composite microsphere material of magnetic hollow according to claim 1 or 6 or 7, its feature
It is, described protective gas is nitrogen or argon.
9. the preparation method of the graphene-based composite microsphere material of magnetic hollow according to claim 1 is it is characterised in that height
The heating rate of warm roasting process is 0.5 ~ 10 DEG C/min, and the flow velocity of protective gas is 50 ~ 150mL/min.
10. application in dye wastewater treatment for a kind of graphene-based composite microsphere material of magnetic hollow of claim 1 preparation.
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| CN108419426A (en) * | 2018-03-05 | 2018-08-17 | 沈阳航空航天大学 | Coated with silica magnetic graphene tiny balloon and its magnanimity preparation method |
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