CN106744896B - A kind of preparation method of closed pore graphene oxide sponge - Google Patents

A kind of preparation method of closed pore graphene oxide sponge Download PDF

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CN106744896B
CN106744896B CN201710042236.5A CN201710042236A CN106744896B CN 106744896 B CN106744896 B CN 106744896B CN 201710042236 A CN201710042236 A CN 201710042236A CN 106744896 B CN106744896 B CN 106744896B
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graphene oxide
closed pore
sponge
distilled water
speed
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CN201710042236.5A
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CN106744896A (en
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矫维成
丁国民
王荣国
郝立峰
徐忠海
刘文博
杨帆
赫晓东
刘伟光
杨双赫
孔嘉珣
刘家印
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哈尔滨工业大学
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    • C01INORGANIC CHEMISTRY
    • C01PINDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00Particle morphology
    • C01P2004/01Particle morphology depicted by an image
    • C01P2004/03Particle morphology depicted by an image obtained by SEM

Abstract

A kind of preparation method of closed pore graphene oxide sponge, it is related to a kind of preparation method of closed pore graphene oxide sponge.The purpose of the present invention will solve the problems, such as that the prior art can not prepare closed pore graphene oxide sponge.Preparation method:One, graphene oxide is prepared;Two, graphene oxide lotion is prepared;Three, it is freeze-dried, obtains closed pore graphene oxide sponge.Advantage:One, natural graphite is aoxidized using strong oxidizer, its surface is made to generate oxygen-containing functional group, and then expanded stripping and obtain graphene oxide.Two, environmentally friendly, it is simply, at low cost, it repeats, it is easily controllable, it can be achieved that technology produces.Closed pore graphene oxide sponge prepared by the present invention is graphene in heat-barrier material, and the aspect that designs and prepares of sound-absorbing material and hydrophobic material peculiar to vessel provides a potential application prospect.

Description

A kind of preparation method of closed pore graphene oxide sponge
Technical field
The present invention relates to a kind of preparation methods of closed pore graphene oxide sponge.
Background technology
Since 2004 are found, graphene is counted as always the material of great potential.Graphene be by carbon atom with SP2 is keyed the cellular 2D monolayers structure to be formed, since it shows high electrical and thermal conductivity, excellent machinery Intensity, the properties such as great specific surface area so that graphene is widely used in multiple fields, such as super capacitor, biology Chemical sensor, catalyst carrier, transparent conductive film etc..But graphene film interlayer makes there are strong π-π sucking actions Graphene be easily stacked, form various forms of microstructures to hinder graphene, limit its Application in industrialized production.But itself for material, microstructure directly affects its physical property, in order to obtain Material with multiple performance, regulation and control microstructure are imperative.
Graphene oxide is to introduce oxygen-containing official in the interlayer of graphite after strong acid and strong oxidizer are aoxidized by graphite It can roll into a ball, then carry out the water-soluble material that ultrasound stripping obtains.GO is mainly by fragrant carbon atom plane and a variety of oxygen-containing functions Group's composition, such as hydroxyl, carboxyl, epoxy group and carbonyl, the structural model for the graphene oxide being widely accepted now is thought, in GO Carboxyl is located at the edge of plane, and hydroxyl and epoxy group are predominantly located in face.The introducing of oxygen-containing functional group had both hindered GO lamellas Stacking, increase its dispersibility in water, and possibility is provided for the chemistry functional of GO.
Due to carboxyl, the presence of the hydrophilic functional groups such as hydroxyl, GO is seen as hydrophilic material all the time.Until 2010, Jaemyung Kim, etc. had found that GO not only has hydrophily, while having lipophile, this is mainly due to GO's Hydrophobic carbon skeleton, therefore GO is seen as amphiphilic high molecular material.Based on its amphiphilic character, GO interface from Assembling causes the research of numerous scientific research personnel.
Invention content
The purpose of the present invention will solve the problems, such as that the prior art can not prepare closed pore graphene oxide sponge, and provide a kind of The preparation method of closed pore graphene oxide sponge.
A kind of preparation method of closed pore graphene oxide sponge, is specifically realized by the following steps:
One, graphene oxide is prepared:
Natural graphite is added in the concentrated sulfuric acid that mass fraction is 98% under condition of ice bath, and low whipping speed is 10min~40min is stirred under 300r/min~400r/min, then by KMnO4Divide 4~6 additions, and low whipping speed is 300r/min~400r/min stirs 2h~2.5h, then changes ice bath, is placed in the water bath with thermostatic control that temperature is 30~40 DEG C, Low whipping speed is that 300r/min~400r/min stirs 30min~60min, then walks around and move to the water bath with thermostatic control that temperature is 80 DEG C In pot, and low whipping speed is persistently overheating to 80 DEG C under the conditions of 300r/min~400r/min, then distilled water I is divided 4~6 times It is added, low whipping speed is that 300r/min~400r/min stirs 15min~20min, then is diluted with distilled water II, then adds Enter and dilute hydrogen peroxide, is then ultrasonically treated 1h~2h, then 10min is centrifuged for 8000r/min in centrifugal speed, it is solid to obtain centrifugation Then body carries out centrifuge washing using distilled water to centrifugal solids, solid after being washed until washing to filtrate pH value is 5~6 Body;7h~8h is dried to solid after washing at 60 DEG C in vacuum tank, obtains graphene oxide powder;The mass fraction is The volume of 98% concentrated sulfuric acid and the mass ratio of natural graphite are 23mL:1g;The KMnO4Mass ratio with natural graphite is 6: 1;The volume of the distilled water I and the mass ratio of natural graphite are 80mL:1g;The volume of the distilled water II and natural graphite Mass ratio is 60mL:1g;The hydrogen peroxide and distilled water III that the dilution hydrogen peroxide is 30% by mass fraction mix, and The volume ratio of the hydrogen peroxide that mass fraction is 30% and distilled water III is 10.81:60;
Two, graphene oxide lotion is prepared:
Graphene oxide powder is added in deionized water, and is ultrasonically treated 1h~2h, is then added polyvinyl alcohol, and Temperature is 90 DEG C and mixing speed is 1000r/min~1800r/min stirring 20min~30min, and it is 40 DEG C to be subsequently placed in temperature In water-bath, NaCl and diphenyl ether are added, finally the high speed shear 1h under the rate of 8000r/min~20000r/min, obtains Graphene oxide lotion;The quality of the graphene oxide powder and the volume ratio of deionized water are 5mg:1mL;The oxidation stone The mass ratio of black alkene powder and polyvinyl alcohol is 5:1;The mass ratio of the graphene oxide powder and NaCl are 5:(3~4);Institute The volume ratio of the quality and diphenyl ether of stating graphene oxide powder is 50mg:2mL;
Three, it is freeze-dried:
It is first -60 DEG C by graphene oxide emulsion freeze 30min in temperature, is freezed at being then -60 DEG C in temperature dry Dry 3 days, freeze-drying graphene oxide block is obtained, then freeze-drying graphene oxide block is placed in vacuum drying chamber vacuum at 80 DEG C Drying for 24 hours, obtains closed pore graphene oxide sponge.
Advantage of the present invention:One, graphene oxide is prepared using improvement Hummers methods.The principle of oxidation process is using strong Oxidant aoxidizes natural graphite, its surface is made to generate oxygen-containing functional group, and then expands stripping and obtain graphene oxide. Two, select diphenyl ether as oil phase, main there are two reasons:First, the fusing point of diphenyl ether is higher (28 DEG C), in the freezing in later stage In the process, diphenyl ether can first solidify, and advantageously form regular hole-closing structure;Second, contain phenyl ring in diphenyl ether, so as to Phenyl ring in enough and graphene oxide forms π-π attractions, is conducive to graphene oxide and is adsorbed at two-phase interface.But due to Graphene oxide can ionize out COO in aqueous solution-So that there are strong electrostatic repulsion forces between lamella, hinder oxidation Stacking of the graphene sheet layer at water-oil interface, destroys lotion regularity.In order to reduce the electrostatic between graphene oxide layer Repel, by adding sodium chloride, introduces a large amount of counter ion Na+To combine COO-, to weaken the repulsion of graphene oxide layer Power increases lamella in the stacking of interface, greatly improves the stability of solution.While in order to increase finally obtained sponge Intensity, introducing polyvinyl alcohol is enhanced, finally by the graphite oxide that different-grain diameter size is made under control shear rate Alkene lotion.Three, graphene oxide lotion is freezed in the environment of -60 DEG C, is then freeze-dried, ensure cost system It is standby go out closed pore graphene oxide sponge.Four, the method for the present invention environmental protection, it is simply, at low cost, it repeats, it is easily controllable, it can be achieved that work Skill metaplasia is produced.
Closed pore graphene oxide sponge prepared by the present invention is graphene in heat-barrier material, sound-absorbing material peculiar to vessel and hydrophobic The aspect that designs and prepares of material provides a potential application prospect.
Description of the drawings
Fig. 1 is photo after the graphene oxide lotion that 1 step 2 of embodiment obtains is stood for 24 hours;
Fig. 2 is photo after the graphene oxide lotion that 4 step 2 of embodiment obtains is stood for 24 hours;
Fig. 3 is closed pore graphene oxide sponge photo prepared by embodiment 1;
Fig. 4 is graphene oxide sponge photo prepared by embodiment 4;
Fig. 5 is closed pore graphene oxide sponge SEM figures prepared by embodiment 1;
Fig. 6 is graphene oxide sponge SEM figures prepared by embodiment 4;
Fig. 7 is closed pore graphene oxide sponge photo prepared by embodiment 2;
Fig. 8 is closed pore graphene oxide sponge photo prepared by embodiment 3;
Fig. 9 is closed pore graphene oxide sponge photo prepared by embodiment 1;
Figure 10 is closed pore graphene oxide sponge SEM figures prepared by embodiment 2;
Figure 11 is closed pore graphene oxide sponge SEM figures prepared by embodiment 3;
Figure 12 is closed pore graphene oxide sponge SEM figures prepared by embodiment 1.
Specific implementation mode
Specific implementation mode one:Present embodiment is a kind of preparation method of closed pore graphene oxide sponge, is specifically pressed What following steps were completed:
One, graphene oxide is prepared:
Natural graphite is added in the concentrated sulfuric acid that mass fraction is 98% under condition of ice bath, and low whipping speed is 10min~40min is stirred under 300r/min~400r/min, then by KMnO4Divide 4~6 additions, and low whipping speed is 300r/min~400r/min stirs 2h~2.5h, then changes ice bath, is placed in the water bath with thermostatic control that temperature is 30~40 DEG C, Low whipping speed is that 300r/min~400r/min stirs 30min~60min, then walks around and move to the water bath with thermostatic control that temperature is 80 DEG C In pot, and low whipping speed is persistently overheating to 80 DEG C under the conditions of 300r/min~400r/min, then distilled water I is divided 4~6 times It is added, low whipping speed is that 300r/min~400r/min stirs 15min~20min, then is diluted with distilled water II, then adds Enter and dilute hydrogen peroxide, is then ultrasonically treated 1h~2h, then 10min is centrifuged for 8000r/min in centrifugal speed, it is solid to obtain centrifugation Then body carries out centrifuge washing using distilled water to centrifugal solids, solid after being washed until washing to filtrate pH value is 5~6 Body;7h~8h is dried to solid after washing at 60 DEG C in vacuum tank, obtains graphene oxide powder;The mass fraction is The volume of 98% concentrated sulfuric acid and the mass ratio of natural graphite are 23mL:1g;The KMnO4Mass ratio with natural graphite is 6: 1;The volume of the distilled water I and the mass ratio of natural graphite are 80mL:1g;The volume of the distilled water II and natural graphite Mass ratio is 60mL:1g;The hydrogen peroxide and distilled water III that the dilution hydrogen peroxide is 30% by mass fraction mix, and The volume ratio of the hydrogen peroxide that mass fraction is 30% and distilled water III is 10.81:60;
Two, graphene oxide lotion is prepared:
Graphene oxide powder is added in deionized water, and is ultrasonically treated 1h~2h, is then added polyvinyl alcohol, and Temperature is 90 DEG C and mixing speed is 1000r/min~1800r/min stirring 20min~30min, and it is 40 DEG C to be subsequently placed in temperature In water-bath, NaCl and diphenyl ether are added, finally the high speed shear 1h under the rate of 8000r/min~20000r/min, obtains Graphene oxide lotion;The quality of the graphene oxide powder and the volume ratio of deionized water are 5mg:1mL;The oxidation stone The mass ratio of black alkene powder and polyvinyl alcohol is 5:1;The mass ratio of the graphene oxide powder and NaCl are 5:(3~4);Institute The volume ratio of the quality and diphenyl ether of stating graphene oxide powder is 50mg:2mL;
Three, it is freeze-dried:
It is first -60 DEG C by graphene oxide emulsion freeze 30min in temperature, is freezed at being then -60 DEG C in temperature dry Dry 3 days, freeze-drying graphene oxide block is obtained, then freeze-drying graphene oxide block is placed in vacuum drying chamber vacuum at 80 DEG C Drying for 24 hours, obtains closed pore graphene oxide sponge.
Graphene oxide is prepared using improvement Hummers methods in present embodiment step 1.The principle of oxidation process is to adopt Natural graphite is aoxidized with strong oxidizer, its surface is made to generate oxygen-containing functional group, and then expands stripping and obtains graphite oxide Alkene.
Preparation principle is as follows in present embodiment step 2:Since graphene oxide is with amphiphilic so that it can be in water It is adsorbed the interface of oil.Select diphenyl ether as oil phase, main there are two reasons:First, the fusing point of diphenyl ether is higher by (28 DEG C), in the refrigerating process in later stage, diphenyl ether can first solidify, and advantageously form regular hole-closing structure;Second, diphenyl ether In contain phenyl ring, so as to in graphene oxide phenyl ring formed π-π attractions, be conducive to graphene oxide in two phase boundaries It is adsorbed at face.But since graphene oxide can ionize out COO in aqueous solution-So that there are strong electrostatic between lamella Repulsive force hinders stacking of the graphene oxide layer at water-oil interface, destroys lotion regularity.In order to reduce oxidation stone The electrostatic repulsion of black alkene piece interlayer introduces a large amount of counter ion Na by adding sodium chloride+To combine COO-, to weaken oxidation The repulsive force of graphene sheet layer increases lamella in the stacking of interface, greatly improves the stability of solution.While in order to increase Add the intensity of finally obtained sponge, introducing polyvinyl alcohol is enhanced, and different grains are finally made under different shear rates The graphene oxide lotion of diameter size.
Graphene oxide lotion is freezed in the environment of -60 DEG C in present embodiment step 2, is then carried out cold It is lyophilized dry, ensures that cost prepares closed pore graphene oxide sponge.
Specific implementation mode two:The difference of present embodiment and specific implementation mode one is:Steaming described in step 1 Distilled water I, distilled water II and distilled water III are distilled water.Other are same as the specific embodiment one.
Specific implementation mode three:One of present embodiment and specific implementation mode one or two difference are:It will in step 1 KMnO45 equivalent are divided to be added.Other are the same as one or two specific embodiments.
Specific implementation mode four:One of present embodiment and specific implementation mode one to three difference are:It will in step 1 I points of 5 equivalent of distilled water are added.Other are identical as specific implementation mode one to three.
Specific implementation mode five:One of present embodiment and specific implementation mode one to four difference are:In step 2 High speed shear 1h under the rate of 8000r/min.Other are identical as specific implementation mode one to four.
Specific implementation mode six:One of present embodiment and specific implementation mode one to five difference are:In step 2 High speed shear 1h under the rate of 12000r/min.Other are identical as specific implementation mode one to five.
Specific implementation mode seven:One of present embodiment and specific implementation mode one to six difference are:In step 2 High speed shear 1h under the rate of 20000r/min.Other are identical as specific implementation mode one to six.
Specific implementation mode eight:One of present embodiment and specific implementation mode one to seven difference are:It will in step 3 Freeze-drying graphene oxide block is placed in vacuum drying chamber, and 4h is dried in vacuo at being 80 DEG C in temperature.Other and specific embodiment party Formula one to seven is identical.
The content of present invention is not limited only to the content of the respective embodiments described above, the group of one of them or several specific implementation modes Contract sample can also realize the purpose of invention.
Using following verification experimental verifications effect of the present invention
Embodiment 1:A kind of preparation method of closed pore graphene oxide sponge, is specifically realized by the following steps:
One, graphene oxide is prepared:
1g natural graphites are added in the concentrated sulfuric acid that 23mL mass fractions are 98% under condition of ice bath, and low whipping speed To stir 20min under 300r/min, then by 6g KMnO45 equivalent are divided to be added, and low whipping speed is that 300r/min is stirred Then 2.5h changes ice bath, be placed in the water bath with thermostatic control that temperature is 35 DEG C, and low whipping speed is that 300r/min stirs 45min, It walks around and is moved in the thermostat water bath that temperature is 80 DEG C again, and low whipping speed is persistently overheating to 80 under the conditions of 300r/min DEG C, then 80mL 5 equivalent of distillation moisture are added, low whipping speed is that 300r/min stirs 20min, then with 60mL distilled water into Row dilution, adds dilution hydrogen peroxide, is then ultrasonically treated 1.5h, then centrifuge 10min in centrifugal speed for 8000r/min, obtains To centrifugal solids, centrifuge washing then is carried out until washing to filtrate pH value is 6 to centrifugal solids using distilled water and is washed Wash rear solid;8h is dried to solid after washing at 60 DEG C in vacuum tank, obtains graphene oxide powder;The dilution hydrogen peroxide The hydrogen peroxide and 60mL distilled water for being 30% by 10.81mL mass fractions mix;
Two, graphene oxide lotion is prepared:
50mg graphene oxide powders are added in 10mL deionized waters, and are ultrasonically treated 1.5h, it is poly- that 10mg is then added Vinyl alcohol, and be 90 DEG C in temperature and mixing speed is that 1500r/min stirs 20min, being subsequently placed in temperature is in 40 DEG C of water-baths, 30mg NaCl and 2mL diphenyl ether is added, finally the high speed shear 1h under the rate of 20000r/min, obtains graphene oxide Lotion;
Three, it is freeze-dried:
It is first -60 DEG C by graphene oxide emulsion freeze 30min in temperature, is freezed at being then -60 DEG C in temperature dry Dry 3 days, freeze-drying graphene oxide block is obtained, then freeze-drying graphene oxide block is placed in vacuum drying chamber vacuum at 80 DEG C Drying for 24 hours, obtains closed pore graphene oxide sponge.
The present embodiment in freezing dry process, diphenyl ether drying frame lower layer's regelation, so the present invention can be with Effective recycling diphenyl ether, is a kind of preparation method of green.
Embodiment 2:The present embodiment and the difference of embodiment 1 are:It is cut at a high speed under the rate of 8000r/min in step 2 Cut 1h.Other are same as Example 1.
Embodiment 3:The present embodiment and the difference of embodiment 1 are:In step 2 under the rate of 12000r/min at a high speed Shear 1h.Other are same as Example 1.
Embodiment 4:Without NaCl contrast tests:It is specifically realized by the following steps:
One, graphene oxide is prepared:
1g natural graphites are added in the concentrated sulfuric acid that 23mL mass fractions are 98% under condition of ice bath, and low whipping speed To stir 20min under 300r/min, then by 6g KMnO45 equivalent are divided to be added, and low whipping speed is that 300r/min is stirred Then 2.5h changes ice bath, be placed in the water bath with thermostatic control that temperature is 35 DEG C, and low whipping speed is that 300r/min stirs 45min, It walks around and is moved in the thermostat water bath that temperature is 80 DEG C again, and low whipping speed is persistently overheating to 80 under the conditions of 300r/min DEG C, then 80mL 5 equivalent of distillation moisture are added, low whipping speed is that 300r/min stirs 20min, then with 60mL distilled water into Row dilution, adds dilution hydrogen peroxide, is then ultrasonically treated 1.5h, then centrifuge 10min in centrifugal speed for 8000r/min, obtains To centrifugal solids, centrifuge washing then is carried out until washing to filtrate pH value is 6 to centrifugal solids using distilled water and is washed Wash rear solid;8h is dried to solid after washing at 60 DEG C in vacuum tank, obtains graphene oxide powder;The dilution hydrogen peroxide The hydrogen peroxide and 60mL distilled water for being 30% by 10.81mL mass fractions mix;
Two, graphene oxide lotion is prepared:
50mg graphene oxide powders are added in 10mL deionized waters, and are ultrasonically treated 1.5h, it is poly- that 10mg is then added Vinyl alcohol, and be 90 DEG C in temperature and mixing speed is that 1500r/min stirs 20min, being subsequently placed in temperature is in 40 DEG C of water-baths, 2mL diphenyl ether is added, finally the high speed shear 1h under the rate of 20000r/min, obtains graphene oxide lotion;
Three, it is freeze-dried:
It is first -60 DEG C by graphene oxide emulsion freeze 30min in temperature, is freezed at being then -60 DEG C in temperature dry Dry 3 days, freeze-drying graphene oxide block is obtained, then freeze-drying graphene oxide block is placed in vacuum drying chamber vacuum at 80 DEG C Drying for 24 hours, obtains graphene oxide sponge.
The graphene oxide lotion that 1 step 2 of a certain amount of embodiment obtains and the oxygen that 4 step 2 of embodiment obtains are taken respectively Graphite alkene lotion is placed in vial, is stood for 24 hours, as a result as depicted in figs. 1 and 2, Fig. 1 is that 1 step 2 of embodiment obtains Photo after graphene oxide lotion is stood for 24 hours, Fig. 2 be the obtained graphene oxide lotion of 4 step 2 of embodiment stand for 24 hours afterwards according to Piece, by Fig. 1 and Fig. 2:Fig. 1 is stood for 24 hours afterwards without lamination, illustrates that emulsion system can be remarkably reinforced in sodium chloride Stability.
Fig. 3 is closed pore graphene oxide sponge photo prepared by embodiment 1, and Fig. 4 is graphene oxide prepared by embodiment 4 Sponge photo, by Fig. 3 and Fig. 4 comparisons it is found that the graphene oxide sponge containing sodium chloride is able to maintain that in freeze-drying Shape illustrates that sodium chloride is of great significance to the structure for stablizing closed pore sponge.Stable hole-closing structure can be increased.
Fig. 5 is closed pore graphene oxide sponge SEM figures prepared by embodiment 1;Fig. 6 is graphite oxide prepared by embodiment 4 Alkene sponge SEM figures;Show that the sponge containing sodium chloride has complete hole-closing structure by Fig. 5 and Fig. 6 comparisons, illustrates sodium chloride The hole-closing structure of graphene oxide sponge can be stablized.
Fig. 7 is closed pore graphene oxide sponge photo prepared by embodiment 2, and Fig. 8 is closed pore oxidation stone prepared by embodiment 3 Black alkene sponge photo, Fig. 9 are closed pore graphene oxide sponge photos prepared by embodiment 1, show different shearing speed by comparison The graphene oxide sponge to differ to aperture can be obtained under rate, illustrate the grain size of graphene oxide closed pore sponge prepared by the present invention It is easily controllable.
Figure 10 is closed pore graphene oxide sponge SEM figures prepared by embodiment 2, and Figure 11 is closed pore oxygen prepared by embodiment 3 Graphite alkene sponge SEM figures, Figure 12 are closed pore graphene oxide sponge SEM figures prepared by embodiment 1, show to shear by comparison Rate is higher, and the aperture of graphene oxide sponge obtained is smaller, illustrates graphene oxide closed pore sponge prepared by the present invention Grain size is easily controllable.

Claims (8)

1. a kind of preparation method of closed pore graphene oxide sponge, it is characterised in that it was specifically realized by the following steps:
One, graphene oxide is prepared:
Natural graphite is added in the concentrated sulfuric acid that mass fraction is 98% under condition of ice bath, and low whipping speed is 300r/min 10min~40min is stirred under~400r/min, then by KMnO4Points of 4~6 times additions, and low whipping speed be 300r/min~ 400r/min stirs 2h~2.5h, then changes ice bath, is placed in the water bath with thermostatic control that temperature is 30~40 DEG C, low whipping speed 30min~60min is stirred for 300r/min~400r/min, is transferred in the thermostat water bath that temperature is 80 DEG C, and stirring It is persistently overheating to 80 DEG C under the conditions of 300r/min~400r/min to mix speed, then by I points of 4~6 additions of distilled water, is being stirred Speed is that 300r/min~400r/min stirs 15min~20min, then is diluted with distilled water II, adds dilution dioxygen Then water is ultrasonically treated 1h~2h, then centrifuges 10min in centrifugal speed for 8000r/min, obtain centrifugal solids, then utilize Distilled water carries out centrifuge washing to centrifugal solids, until washing to filtrate pH value is 5~6, solid after being washed;In vacuum tank 7h~8h is dried to solid after washing at interior 60 DEG C, obtains graphene oxide powder;The concentrated sulfuric acid that the mass fraction is 98% Volume and natural graphite mass ratio be 23mL:1g;The KMnO4Mass ratio with natural graphite is 6:1;The distilled water The volume of I and the mass ratio of natural graphite are 80mL:1g;The volume of the distilled water II and the mass ratio of natural graphite are 60mL:1g;The hydrogen peroxide and distilled water III that the dilution hydrogen peroxide is 30% by mass fraction mix, and mass fraction It is 10.81 for 30% hydrogen peroxide and the volume ratio of distilled water III:60;
Two, graphene oxide lotion is prepared:
Graphene oxide powder is added in deionized water, and is ultrasonically treated 1h~2h, polyvinyl alcohol is then added, and in temperature It is that 1000r/min~1800r/min stirs 20min~30min for 90 DEG C and mixing speed, it is 40 DEG C of water-baths to be subsequently placed in temperature In, NaCl and diphenyl ether are added, finally the high speed shear 1h under the rate of 8000r/min~20000r/min, is aoxidized Graphene emulsion;The quality of the graphene oxide powder and the volume ratio of deionized water are 5mg:1mL;The graphene oxide The mass ratio of powder and polyvinyl alcohol is 5:1;The mass ratio of the graphene oxide powder and NaCl are 5:(3~4);The oxygen The quality of graphite alkene powder and the volume ratio of diphenyl ether are 50mg:2mL;
Three, it is freeze-dried:
First temperature be -60 DEG C by graphene oxide emulsion freeze 30min, then temperature be -60 DEG C at be freeze-dried 3 It, obtains freeze-drying graphene oxide block, then freeze-drying graphene oxide block is placed in vacuum drying chamber at 80 DEG C that vacuum is done It is dry for 24 hours, obtain closed pore graphene oxide sponge.
2. a kind of preparation method of closed pore graphene oxide sponge according to claim 1, it is characterised in that in step 1 Distilled water I, distilled water II and the distilled water III is distilled water.
3. a kind of preparation method of closed pore graphene oxide sponge according to claim 1, it is characterised in that in step 1 By KMnO45 equivalent are divided to be added.
4. a kind of preparation method of closed pore graphene oxide sponge according to claim 1, it is characterised in that in step 1 I points of 5 equivalent of distilled water are added.
5. a kind of preparation method of closed pore graphene oxide sponge according to claim 1, it is characterised in that in step 2 The high speed shear 1h under the rate of 8000r/min.
6. a kind of preparation method of closed pore graphene oxide sponge according to claim 1, it is characterised in that in step 2 The high speed shear 1h under the rate of 12000r/min.
7. a kind of preparation method of closed pore graphene oxide sponge according to claim 1, it is characterised in that in step 2 The high speed shear 1h under the rate of 20000r/min.
8. a kind of preparation method of closed pore graphene oxide sponge according to claim 1, it is characterised in that in step 3 Freeze-drying graphene oxide block is placed in vacuum drying chamber, 4h is dried in vacuo at being 80 DEG C in temperature.
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Interconnectivity of Macroporous Hydrogels Prepared via Graphene Oxide-Stabilized Pickering High Internal Phase Emulsions;Wenyuan Yi et al.;《Langmuir》;20160111;第32卷;第982-990页 *
Zheng Zheng et al..Macroporous Graphene Oxide−Polymer Composite Prepared through Pickering High Internal Phase Emulsions.《ACS Applied Materials & Interfaces》.2013,第5卷第7974−7982页. *

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