CN106744896A - 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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CN106744896A
CN106744896A CN201710042236.5A CN201710042236A CN106744896A CN 106744896 A CN106744896 A CN 106744896A CN 201710042236 A CN201710042236 A CN 201710042236A CN 106744896 A CN106744896 A CN 106744896A
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graphene oxide
closed pore
speed
sponge
distilled water
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CN201710042236.5A
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CN106744896B (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 prior art cannot prepare closed pore graphene oxide sponge.Preparation method:First, graphene oxide is prepared;2nd, graphene oxide emulsion is prepared;3rd, freeze-drying, obtains closed pore graphene oxide sponge.Advantage:First, native graphite is aoxidized using strong oxidizer, its surface is produced oxygen-containing functional group, and then expansion stripping obtains graphene oxide.2nd, environmental protection, simply, low cost is repeated, it is easy to control, and is capable of achieving technology production.Closed pore graphene oxide sponge prepared by the present invention is Graphene in heat-barrier material, design and preparation aspect one potential application prospect of offer of sound-absorbing material peculiar to vessel and hydrophobic material.

Description

A kind of preparation method of closed pore graphene oxide sponge
Technical field
The present invention relates to a kind of preparation method of closed pore graphene oxide sponge.
Background technology
Since being found from 2004, Graphene is counted as the material of great potential always.Graphene be by carbon atom with SP2 is bonded and connects the cellular 2D monolayers structure to be formed, because it shows high electrical and thermal conductivity, excellent machinery The properties such as intensity, great specific surface area so that Graphene is widely used in multiple fields, such as super capacitor, it is biological Chemical sensor, catalyst carrier, transparent conductive film etc..But be present strong π-π sucking actions in graphene film interlayer, make Graphene be easily stacked, form various forms of microstructures so as to hinder Graphene, limit its Application in industrialized production.But, microstructure directly affects its physical property for material itself, in order to obtain Material with multiple performance, regulation and control microstructure is imperative.
Graphene oxide is to introduce oxygen-containing official in the interlayer of graphite after strong acid and strong oxidizer are aoxidized by graphite Can roll into a ball, then carry out ultrasound and peel off the water-soluble material for obtaining.The main carbon atom planes and various oxygen-containing functions by fragrance of GO Group's composition, such as hydroxyl, carboxyl, epoxy radicals and carbonyl, the structural model of the graphene oxide being widely accepted now is thought, in GO Carboxyl is located at the edge of plane, and hydroxyl and epoxy radicals are predominantly located in face.The introducing of oxygen-containing functional group, had both hindered GO lamellas Stacking, increased its dispersiveness in water, and for the chemistry functional of GO provides possibility.
Due to carboxyl, the presence of the hydrophilic functional group 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 amphipathic macromolecular material.Based on its amphiphilic character, GO interface from Assembling causes the research of numerous scientific research personnel.
The content of the invention
The purpose of the present invention will solve the problems, such as that prior art cannot 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:
First, graphene oxide is prepared:
In being 98% concentrated sulfuric acid by native graphite addition mass fraction under the condition of ice bath, and low whipping speed is 10min~40min is stirred under 300r/min~400r/min, then by KMnO4Divide 4~6 times and add, 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 the water bath with thermostatic control for moving to that temperature is 80 DEG C of walking around 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 Add, low whipping speed is that 300r/min~400r/min stirs 15min~20min, then is diluted with distilled water II, then is added Enter and dilute hydrogen peroxide, then ultrasonically treated 1h~2h, then be that 8000r/min is centrifuged 10min in centrifugal speed, obtain centrifugation solid Then centrifugal solids are carried out centrifuge washing by body using distilled water, solid after being washed washing to filtrate pH value is 5~6 Body;In the vacuum tank at 60 DEG C to washing after solid dry 7h~8h, obtain graphene oxide powder;The mass fraction is The volume of 98% concentrated sulfuric acid is 23mL with the mass ratio of native graphite:1g;The KMnO4It is 6 with the mass ratio of native graphite: 1;The volume of the distilled water I is 80mL with the mass ratio of native graphite:1g;The volume of the distilled water II and native graphite Mass ratio is 60mL:1g;The dilution hydrogen peroxide is mixed by hydrogen peroxide that mass fraction is 30% and distilled water III, and Mass fraction is 30% hydrogen peroxide and the volume ratio of distilled water III is 10.81:60;
2nd, graphene oxide emulsion is prepared:
During graphene oxide powder added into deionized water, and ultrasonically treated 1h~2h is subsequently adding polyvinyl alcohol, and It is that 1000r/min~1800r/min stirs 20min~30min with mixing speed that temperature is 90 DEG C, is subsequently placed in temperature for 40 DEG C In water-bath, NaCl and diphenyl ether are added, finally the high speed shear 1h under the speed of 8000r/min~20000r/min, obtains Graphene oxide emulsion;The quality of the graphene oxide powder is 5mg with the volume ratio of deionized water:1mL;The oxidation stone Black alkene powder is 5 with the mass ratio of polyvinyl alcohol:1;The graphene oxide powder is 5 with the mass ratio of NaCl:(3~4);Institute The volume ratio of the quality and diphenyl ether of stating graphene oxide powder is 50mg:2mL;
3rd, freeze-drying:
First in temperature for -60 DEG C by graphene oxide emulsion freeze 30min, freezing is dry at being then -60 DEG C in temperature Dry 3 days, lyophilized graphene oxide block is obtained, then lyophilized graphene oxide block is placed in vacuum drying chamber vacuum at 80 DEG C 24h is dried, closed pore graphene oxide sponge is obtained.
Advantage of the present invention:First, graphene oxide is prepared using improvement Hummers methods.The principle of oxidizing process is using strong Oxidant is aoxidized native graphite, its surface is produced oxygen-containing functional group, and then expansion stripping obtains graphene oxide. 2nd, from diphenyl ether as oil phase, mainly there are two reasons:First, the fusing point of diphenyl ether is (28 DEG C) higher, in the freezing in later stage During, diphenyl ether can first solidify, and advantageously form regular hole-closing structure;Second, phenyl ring is contained in diphenyl ether, so as to Phenyl ring in enough and graphene oxide forms π-π attractions, is conducive to graphene oxide to be adsorbed at two-phase interface.But due to Graphene oxide can ionize out COO in aqueous-So that there are strong electrostatic repulsion forces between lamella, hinder oxidation Stacking of the graphene sheet layer at water-oil interface, destroys emulsion regularity.In order to reduce the electrostatic between graphene oxide layer Repel, by adding sodium chloride, introduce substantial amounts of counter ion Na+To combine COO-, so as to weaken the repulsion of graphene oxide layer Power, increases lamella in the stacking of interface, greatly improves the stability of solution.Simultaneously in order to increase the sponge for finally giving Intensity, introducing polyvinyl alcohol is strengthened, finally by the graphite oxide that different-grain diameter size is obtained under control shear rate Alkene emulsion.3rd, graphene oxide emulsion is freezed in the environment of -60 DEG C, is then carried out freeze-drying, it is ensured that cost system It is standby go out closed pore graphene oxide sponge.4th, the inventive method environmental protection, simply, low cost is repeated, it is easy to control, and is capable of achieving 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 Design and the preparation aspect of material provide a potential application prospect.
Brief description of the drawings
Fig. 1 is that the graphene oxide emulsion that the step 2 of embodiment 1 is obtained stands photo after 24h;
Fig. 2 is that the graphene oxide emulsion that the step 2 of embodiment 4 is obtained stands photo after 24h;
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 embodiment
Specific embodiment one:Present embodiment is a kind of preparation method of closed pore graphene oxide sponge, is specifically pressed What following steps were completed:
First, graphene oxide is prepared:
In being 98% concentrated sulfuric acid by native graphite addition mass fraction under the condition of ice bath, and low whipping speed is 10min~40min is stirred under 300r/min~400r/min, then by KMnO4Divide 4~6 times and add, 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 the water bath with thermostatic control for moving to that temperature is 80 DEG C of walking around 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 Add, low whipping speed is that 300r/min~400r/min stirs 15min~20min, then is diluted with distilled water II, then is added Enter and dilute hydrogen peroxide, then ultrasonically treated 1h~2h, then be that 8000r/min is centrifuged 10min in centrifugal speed, obtain centrifugation solid Then centrifugal solids are carried out centrifuge washing by body using distilled water, solid after being washed washing to filtrate pH value is 5~6 Body;In the vacuum tank at 60 DEG C to washing after solid dry 7h~8h, obtain graphene oxide powder;The mass fraction is The volume of 98% concentrated sulfuric acid is 23mL with the mass ratio of native graphite:1g;The KMnO4It is 6 with the mass ratio of native graphite: 1;The volume of the distilled water I is 80mL with the mass ratio of native graphite:1g;The volume of the distilled water II and native graphite Mass ratio is 60mL:1g;The dilution hydrogen peroxide is mixed by hydrogen peroxide that mass fraction is 30% and distilled water III, and Mass fraction is 30% hydrogen peroxide and the volume ratio of distilled water III is 10.81:60;
2nd, graphene oxide emulsion is prepared:
During graphene oxide powder added into deionized water, and ultrasonically treated 1h~2h is subsequently adding polyvinyl alcohol, and It is that 1000r/min~1800r/min stirs 20min~30min with mixing speed that temperature is 90 DEG C, is subsequently placed in temperature for 40 DEG C In water-bath, NaCl and diphenyl ether are added, finally the high speed shear 1h under the speed of 8000r/min~20000r/min, obtains Graphene oxide emulsion;The quality of the graphene oxide powder is 5mg with the volume ratio of deionized water:1mL;The oxidation stone Black alkene powder is 5 with the mass ratio of polyvinyl alcohol:1;The graphene oxide powder is 5 with the mass ratio of NaCl:(3~4);Institute The volume ratio of the quality and diphenyl ether of stating graphene oxide powder is 50mg:2mL;
3rd, freeze-drying:
First in temperature for -60 DEG C by graphene oxide emulsion freeze 30min, freezing is dry at being then -60 DEG C in temperature Dry 3 days, lyophilized graphene oxide block is obtained, then lyophilized graphene oxide block is placed in vacuum drying chamber vacuum at 80 DEG C 24h is dried, closed pore graphene oxide sponge is obtained.
Graphene oxide is prepared using improvement Hummers methods in present embodiment step one.The principle of oxidizing process is to adopt Native graphite is aoxidized with strong oxidizer, its surface is produced oxygen-containing functional group, and then expansion stripping obtains graphite oxide Alkene.
Preparation principle is as follows in present embodiment step 2:Due to graphene oxide have it is amphiphilic so that it can be in water Adsorbed the interface of oil.From diphenyl ether as oil phase, mainly 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 such that it is able to and phenyl ring in graphene oxide forms π-π attractions, is conducive to graphene oxide in two phase boundaries Adsorbed at face.But because graphene oxide can ionize out COO in aqueous-So that there is strong electrostatic between lamella Repulsive force, hinders stacking of the graphene oxide layer at water-oil interface, destroys emulsion regularity.In order to reduce oxidation stone The Coulomb repulsion of black alkene piece interlayer, by adding sodium chloride, introduces substantial amounts of counter ion Na+To combine COO-, so as to weaken oxidation The repulsive force of graphene sheet layer, increases lamella in the stacking of interface, greatly improves the stability of solution.Simultaneously in order to increase Plus the intensity of the sponge for finally giving, introducing polyvinyl alcohol is strengthened, and different grains are finally obtained under different shear rates The graphene oxide emulsion of footpath size.
Graphene oxide emulsion is freezed in the environment of -60 DEG C in present embodiment step 2, is then carried out cold It is lyophilized dry, it is ensured that cost prepares closed pore graphene oxide sponge.
Specific embodiment two:Present embodiment is with the difference of specific embodiment one:Steaming described in step one Distilled water I, distilled water II and distilled water III are distilled water.Other are identical with specific embodiment one.
Specific embodiment three:One of present embodiment and specific embodiment one or two difference is:Will in step one KMnO45 equivalent are divided to add.Other are identical with specific embodiment one or two.
Specific embodiment four:One of present embodiment and specific embodiment one to three difference is:Will in step one Distilled water I points of 5 equivalent are added.Other are identical with specific embodiment one to three.
Specific embodiment five:One of present embodiment and specific embodiment one to four difference is:In step 2 High speed shear 1h under the speed of 8000r/min.Other are identical with specific embodiment one to four.
Specific embodiment six:One of present embodiment and specific embodiment one to five difference is:In step 2 High speed shear 1h under the speed of 12000r/min.Other are identical with specific embodiment one to five.
Specific embodiment seven:One of present embodiment and specific embodiment one to six difference is:In step 2 High speed shear 1h under the speed of 20000r/min.Other are identical with specific embodiment one to six.
Specific embodiment eight:One of present embodiment and specific embodiment one to seven difference is:Will in step 3 Lyophilized graphene oxide block is placed in vacuum drying chamber, and 4h is vacuum dried at being 80 DEG C in temperature.Other and specific embodiment party Formula one to seven is identical.
Present invention is not limited only to the content of the respective embodiments described above, the group of one of them or several specific embodiments 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:
First, graphene oxide is prepared:
In being 98% concentrated sulfuric acid by 1g native graphites addition 23mL mass fractions under the condition of ice bath, and low whipping speed To stir 20min under 300r/min, then by 6g KMnO45 equivalent are divided to add, and low whipping speed is that 300r/min is stirred 2.5h, then changes ice bath, is placed in the water bath with thermostatic control that temperature is 35 DEG C, and low whipping speed is that 300r/min stirs 45min, Walk around again in moving to the thermostat water bath that temperature is 80 DEG C, and low whipping speed is persistently overheating to 80 under the conditions of 300r/min DEG C, then 80mL distillation 5 equivalent of moisture are added, low whipping speed is that 300r/min stirs 20min, then is entered with 60mL distilled water Row dilution, adds dilution hydrogen peroxide, then ultrasonically treated 1.5h, then is that 8000r/min is centrifuged 10min in centrifugal speed, obtains To centrifugal solids, centrifugal solids then are carried out with centrifuge washing using distilled water, washing to filtrate pH value is 6, washed Wash rear solid;In the vacuum tank at 60 DEG C to washing after solid dry 8h, obtain graphene oxide powder;The dilution hydrogen peroxide Mixed by hydrogen peroxide and 60mL distilled water that 10.81mL mass fractions are 30%;
2nd, graphene oxide emulsion is prepared:
During 50mg graphene oxide powders are added into 10mL deionized waters, and ultrasonically treated 1.5h is subsequently adding 10mg and gathers Vinyl alcohol, and be that 90 DEG C and mixing speed are that 1500r/min stirs 20min in temperature, is subsequently placed in temperature in 40 DEG C of water-baths, 30mg NaCl and 2mL diphenyl ether is added, finally the high speed shear 1h under the speed of 20000r/min, obtains graphene oxide Emulsion;
3rd, freeze-drying:
First in temperature for -60 DEG C by graphene oxide emulsion freeze 30min, freezing is dry at being then -60 DEG C in temperature Dry 3 days, lyophilized graphene oxide block is obtained, then lyophilized graphene oxide block is placed in vacuum drying chamber vacuum at 80 DEG C 24h is dried, closed pore graphene oxide sponge is obtained.
The present embodiment in freezing dry process, diphenyl ether drying frame lower floor's regelation, so the present invention can be with It is effective to reclaim diphenyl ether, it is a kind of preparation method of green.
Embodiment 2:The present embodiment is with the difference of embodiment 1:Cut at a high speed under the speed of 8000r/min in step 2 Cut 1h.Other are same as Example 1.
Embodiment 3:The present embodiment is with the difference of embodiment 1:In step 2 under the speed of 12000r/min at a high speed Shearing 1h.Other are same as Example 1.
Embodiment 4:Without NaCl contrast tests:It is specifically realized by the following steps:
First, graphene oxide is prepared:
In being 98% concentrated sulfuric acid by 1g native graphites addition 23mL mass fractions under the condition of ice bath, and low whipping speed To stir 20min under 300r/min, then by 6g KMnO45 equivalent are divided to add, and low whipping speed is that 300r/min is stirred 2.5h, then changes ice bath, is placed in the water bath with thermostatic control that temperature is 35 DEG C, and low whipping speed is that 300r/min stirs 45min, Walk around again in moving to the thermostat water bath that temperature is 80 DEG C, and low whipping speed is persistently overheating to 80 under the conditions of 300r/min DEG C, then 80mL distillation 5 equivalent of moisture are added, low whipping speed is that 300r/min stirs 20min, then is entered with 60mL distilled water Row dilution, adds dilution hydrogen peroxide, then ultrasonically treated 1.5h, then is that 8000r/min is centrifuged 10min in centrifugal speed, obtains To centrifugal solids, centrifugal solids then are carried out with centrifuge washing using distilled water, washing to filtrate pH value is 6, washed Wash rear solid;In the vacuum tank at 60 DEG C to washing after solid dry 8h, obtain graphene oxide powder;The dilution hydrogen peroxide Mixed by hydrogen peroxide and 60mL distilled water that 10.81mL mass fractions are 30%;
2nd, graphene oxide emulsion is prepared:
During 50mg graphene oxide powders are added into 10mL deionized waters, and ultrasonically treated 1.5h is subsequently adding 10mg and gathers Vinyl alcohol, and be that 90 DEG C and mixing speed are that 1500r/min stirs 20min in temperature, is subsequently placed in temperature in 40 DEG C of water-baths, 2mL diphenyl ether is added, finally the high speed shear 1h under the speed of 20000r/min, obtains graphene oxide emulsion;
3rd, freeze-drying:
First in temperature for -60 DEG C by graphene oxide emulsion freeze 30min, freezing is dry at being then -60 DEG C in temperature Dry 3 days, lyophilized graphene oxide block is obtained, then lyophilized graphene oxide block is placed in vacuum drying chamber vacuum at 80 DEG C 24h is dried, graphene oxide sponge is obtained.
The graphene oxide emulsion that the step 2 of a certain amount of embodiment 1 obtains and the oxygen that the step 2 of embodiment 2 is obtained are taken respectively Graphite alkene emulsion stands 24h as in vial, and as a result as depicted in figs. 1 and 2, Fig. 1 is that the step 2 of embodiment 1 is obtained Graphene oxide emulsion stands photo after 24h, and Fig. 2 is shone after the graphene oxide emulsion that the step 2 of embodiment 4 is obtained stands 24h Piece, by Fig. 1 and Fig. 2:Fig. 1 is that do not have lamination after standing 24h, illustrates that sodium chloride can be remarkably reinforced emulsion system 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, is contrasted by Fig. 3 and Fig. 4, and the graphene oxide sponge containing sodium chloride is able to maintain that in freeze-drying Shape, illustrates that sodium chloride is significant to stablizing the structure of closed pore sponge.Stabilization 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 schemes;Contrasted by Fig. 5 and Fig. 6 and show that the sponge containing sodium chloride has complete hole-closing structure, illustrate 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 is closed pore graphene oxide sponge photo prepared by embodiment 1, and different shearing speed are shown by contrast The graphene oxide sponge that can differ to aperture under rate, illustrates the particle diameter of the graphene oxide closed pore sponge of present invention preparation 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 schemes, and Figure 12 is closed pore graphene oxide sponge SEM figures prepared by embodiment 1, and shearing is shown by contrast Speed is higher, and the aperture of obtained graphene oxide sponge is smaller, illustrates the graphene oxide closed pore sponge of present invention preparation Particle diameter is easily controllable.

Claims (8)

1. a kind of preparation method of closed pore graphene oxide sponge, it is characterised in that what it was specifically realized by the following steps:
First, graphene oxide is prepared:
In being 98% concentrated sulfuric acid by native graphite addition mass fraction under the 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 It is 300r/min~400r/min stirring 30min~60min, then walks around and move to the thermostat water bath that temperature is 80 DEG C, and Mixing speed is persistently overheating to 80 DEG C under the conditions of 300r/min~400r/min, then by distilled water I points of 4~6 addition, is being stirred Speed is mixed for 300r/min~400r/min stirs 15min~20min, then is diluted with distilled water II, add dilution double Oxygen water, then ultrasonically treated 1h~2h, then be that 8000r/min is centrifuged 10min in centrifugal speed, obtain centrifugal solids, Ran Houli With distilled water centrifugal solids are carried out with centrifuge washing, washing to filtrate pH value is 5~6, solid after being washed;In vacuum 7h~8h is dried to solid after washing at 60 DEG C in case, graphene oxide powder is obtained;The mass fraction is 98% dense sulphur The volume of acid is 23mL with the mass ratio of native graphite:1g;The KMnO4It is 6 with the mass ratio of native graphite:1;The distillation The volume of water I is 80mL with the mass ratio of native graphite:1g;The volume of the distilled water II is with the mass ratio of native graphite 60mL:1g;The dilution hydrogen peroxide is mixed by hydrogen peroxide that mass fraction is 30% and distilled water III, and mass fraction For 30% hydrogen peroxide and the volume ratio of distilled water III are 10.81:60;
2nd, graphene oxide emulsion is prepared:
During graphene oxide powder added into deionized water, and ultrasonically treated 1h~2h is subsequently adding polyvinyl alcohol, and in temperature It is that 1000r/min~1800r/min stirs 20min~30min with mixing speed to be 90 DEG C, is subsequently placed in temperature for 40 DEG C of water-baths In, NaCl and diphenyl ether are added, finally the high speed shear 1h under the speed of 8000r/min~20000r/min, is aoxidized Graphene emulsion;The quality of the graphene oxide powder is 5mg with the volume ratio of deionized water:1mL;The graphene oxide Powder is 5 with the mass ratio of polyvinyl alcohol:1;The graphene oxide powder is 5 with the mass ratio of NaCl:(3~4);The oxygen The quality of graphite alkene powder is 50mg with the volume ratio of diphenyl ether:2mL;
3rd, freeze-drying:
First temperature be -60 DEG C by graphene oxide emulsion freeze 30min, freeze-drying 3 at being then -60 DEG C in temperature My god, obtain lyophilized graphene oxide block, then lyophilized graphene oxide block is placed in vacuum drying chamber vacuum is done at 80 DEG C Dry 24h, obtains closed pore graphene oxide sponge.
2. the preparation method of a kind of closed pore graphene oxide sponge according to claim 1, it is characterised in that in step one Described distilled water I, distilled water II and distilled water III are distilled water.
3. the preparation method of a kind of closed pore graphene oxide sponge according to claim 1, it is characterised in that in step one By KMnO45 equivalent are divided to add.
4. the preparation method of a kind of closed pore graphene oxide sponge according to claim 1, it is characterised in that in step one Distilled water I points of 5 equivalent are added.
5. the preparation method of a kind 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 speed of 8000r/min.
6. the preparation method of a kind 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 speed of 12000r/min.
7. the preparation method of a kind 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 speed of 20000r/min.
8. the preparation method of a kind of closed pore graphene oxide sponge according to claim 1, it is characterised in that in step 3 Lyophilized graphene oxide block is placed in vacuum drying chamber, 4h is vacuum dried at being 80 DEG C in temperature.
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WENYUAN YI ET AL.: "Interconnectivity of Macroporous Hydrogels Prepared via Graphene Oxide-Stabilized Pickering High Internal Phase Emulsions", 《LANGMUIR》 *
ZHENG ZHENG ET AL.: "Macroporous Graphene Oxide−Polymer Composite Prepared through Pickering High Internal Phase Emulsions", 《ACS APPLIED MATERIALS & INTERFACES》 *

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107140631A (en) * 2017-06-09 2017-09-08 哈尔滨工业大学 A kind of preparation method of the super-hydrophobic graphene film of bionic intelligence
CN107140631B (en) * 2017-06-09 2019-07-02 哈尔滨工业大学 A kind of preparation method of the super-hydrophobic graphene film of bionic intelligence
CN108314032A (en) * 2018-04-18 2018-07-24 哈尔滨工业大学 It is a kind of that there is anti-icing and deicing function the graphene-based material of 3 D stereo reticular structure and preparation method thereof

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