CN105885783A - Mesoporous composite material - Google Patents
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- CN105885783A CN105885783A CN201510017415.4A CN201510017415A CN105885783A CN 105885783 A CN105885783 A CN 105885783A CN 201510017415 A CN201510017415 A CN 201510017415A CN 105885783 A CN105885783 A CN 105885783A
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Abstract
The invention discloses a mesoporous composite material. A preparation method of the material comprises preparation of graphite oxide. Hollow ferroferric oxide nano particles are loaded to a graphene sheet layer surface through a solvothermal method, then the graphene sheet layer surface to which hollow nano ferroferric oxide is loaded is coated with polyaniline, a graphene/hollow ferroferric oxide/polyaniline nano composite material is prepared, and finally the mesoporous material is prepared through high-temperature carbonization treatment. The method is convenient and fast, and the material can be used as an electromagnetic wave absorption material and can also be used as an environmental adsorption material.
Description
Technical field
The present invention relates to absorbing material field, in particular a kind of mesoporous composite material.
Background technology
Along with the development of science and technology with electronics industry, increasing electromagenetic wave radiation is present in around us, through research
Showing, excess electromagenetic wave radiation is except causing the generation obstacles such as nervous system, immune system, reproductive system and blood circulation
Outward, in some instances it may even be possible to induction serious disease including all kinds of cancers.It is chronically in electromagnetic wave environment, by electromagnetic wave in human body
The damage of the tissue and organ that damage and have not enough time to self-regeneration can become dynamic disease and become because of long term accumulation, can time serious
Threat to life.
Graphene, due to the single layer structure of its uniqueness make it have ultralight density, big specific surface area, electric conductivity excellent and
The features such as high dielectric constant so that it is become a kind of novel wave-absorbing material.It addition, what oxidized graphenic surface exposed in a large number
Chemical bond is more prone to the dielectric relaxor of outer-shell electron and electromagnetic wave of decaying under the effect of electromagnetic field, is inhaling ripple neck for Graphene
The applications expanding in territory prospect, at the hollow ferriferrous oxide nano-particle of graphenic surface carried magnetic, is possible not only to improve material
Magnetic property, strengthen composite magnetic loss, the beneficially impedance matching of composite, and ferriferrous oxide particles as every
Reduce Graphene from medium and again stack in three-dimensional graphite structure in dry run, stable graphene film Rotating fields is played quite
Important effect.
The technical problem to be solved is for the deficiencies in the prior art, it is provided that a kind of mesoporous composite material.
Technical scheme is as follows:
A kind of mesoporous composite material, it is characterised in that its step is as follows:
Step one, makes graphite a size of 50-200 mesh and obtains graphite powder, add to the hydrochloric acid that mass fraction is 35% molten afterwards
In liquid, stir 30min, use deionized water repeatedly to rinse so that pH value is neutral afterwards, dry stand-by；
By graphite powder, potassium peroxydisulfate and P2O5Adding in concentrated sulphuric acid, form mixture, the pH value of the mixture formed is 1.5,
This mixture is stirred at 60 DEG C 1-2h, then at 80 DEG C, stirs 2-4h, finally with 2 with the ramp of 5 DEG C/min
DEG C/min be warming up to 87 DEG C stirring 1-2h, then use this mixture of distilled water diluting, the pH value of this mixture is diluted to
3.6, place and use after 36h distilled water to filter so that mixture pH value is 6-7, after carry out drying at room temperature, described graphite powder,
Potassium peroxydisulfate, P2O5It is 1-3: 1-2: 1-2: 5-10 with the mass ratio of concentrated sulphuric acid；
Dried mixture is joined stirring 45-60min in concentrated nitric acid so that pH value is 2-4, described dried mixed
Compound is 1-4: 50-100 with the mass ratio of concentrated nitric acid, adds KMnO after stirring at-8 DEG C for the first time4, stir 30min,
At being cooled to-12 DEG C afterwards, second time adds KMnO4, stir 30min, at being finally cooled to-15 DEG C, third time adds
KMnO4, to stir 20min, obtain the graphite mixture of pre-oxidation, described first time adds KMnO4, second time adds KMnO4
KMnO is added with third time4Mass ratio be 1: 2: 3, described dried mixture and total KMnO4Ratio be
1-2∶10-15；
The graphite mixture obtaining pre-oxidation is filtered and dried, is positioned in Muffle furnace and carries out heat treated, the temperature of heat treatment
Degree, for processing 10-20s at 1100 DEG C, processes 15-20s at 1150 DEG C, process 20-30s, obtain expanded graphite at 1180 DEG C；
Step 2, puts into expanded graphite made for step one and is warmed up to 40 DEG C in couveuse, react 3h, subsequently, add with
Consistent amount of first distilled water of graphite mixture volume of pre-oxidation, then reacts 2.5h, by couveuse temperature to 40 DEG C,
Again add after-fractionating water and H2O2Reaction 10-60min, the amount of described after-fractionating water is 1-1.5 times of the first distilled water,
After-fractionating water and H2O2Volume ratio be 4-20: 1, reaction terminate after carry out centrifugation 10min, rotating speed 8000～10000
R/min, centrifugation afterproduct hydrochloric acid solution washs, and the volume of this hydrochloric acid solution is the 10-50 of centrifugation afterproduct volume
Times, finally dialysis obtains graphite oxide in 7-8 days；N-hydroxyl fourth two is added after graphite oxide is used dimethyl sulfoxide ultrasonic dissolution
Acid imide and self-control surface conditioning agent stirs 2h at 35 DEG C, and product carries out sucking filtration, washs, dries, and i.e. obtain surface process
Graphite oxide.
Step 3,
Under room temperature, the graphite oxide obtained in 1g step 2 is joined in the reactor equipped with 500g deionized water, and will reaction
Device is placed in ultrasonic dispersers stirring, stirs 10-15min, uses ammonia regulation aqueous solution to regulate the pH value of system to 11,
And it is warming up to 70 DEG C, then in reactor, add 5-10g sodium borohydride aqueous solution, after keeping sonic oscillation reaction 30～60min,
The temperature of system is down to 15 DEG C, adds 25g p-aminobenzene sulfonic acid, keep sonic oscillation to react 2～4 hours, then stand
React 3 hours, then mixed liquor is carried out sucking filtration to remove solvent, and be washed with deionized more than 2 times, by filtrate weight
Newly it is dispersed in 400～1600g deionized waters, and adds 1～4g hydrazine hydrate, react 12～24 hours at 80 DEG C, product
By sucking filtration, and it is washed with deionized more than 2 times, finally filtrate is dried 24～48 hours and obtains sulfonated graphite；
Step 4, the sulfonated graphite 1-2g obtained by step 3 is carried out at-10-30 DEG C after lyophilization with 1-10g polycyclic oxygen
Ethane-poly(propylene oxide)-poly(ethylene oxide) triblock copolymer is put into ultrasonic disperse in the ethylene glycol of 500ml in the lump and is formed uniformly
First dispersion liquid；Simultaneously by 4-15g by Fecl3·6H2O、Fecl2·4H2O and the mixture of acetyl acetone ferrum composition, 6～25g
Polyvinylpyrrolidone and 10～50gNH4Ac is dissolved in the ethylene glycol of 500-1000mL and forms the second dispersion liquid, by first
Dispersion liquid and the second dispersion liquid mix and blend, and regulate with ammonia, make the settled solution that pH value is 8-10, described
Fecl3·6H2O、Fecl2·4H2The mass ratio of O and acetyl acetone ferrum is 1: 1: 0.5；
Step 5, puts in reactor by the settled solution obtained by 100ml step 3, after sealing, is heated to 150 DEG C,
Insulation 2h, is warming up to 200 DEG C with the heating rate of 2-4 DEG C/min afterwards, is incubated 4h, afterwards with the intensification speed of 3-6 DEG C/min
Rate is warming up to 235 DEG C, is incubated 3h, is then cooled to 200 DEG C of insulation 2h with the cooling rate of 5-7 DEG C/min, the most again with 3-6
DEG C/heating rate of min is warming up to 235 DEG C, it is incubated 7h, after question response completes, reactor is taken out, is allowed to be cooled to room
Temperature, described cooling rate is 3-6 DEG C/min, by the black powder centrifugation 10min of gained, rotating speed 8000～10000r/min,
Use dehydrated alcohol and deionized water respectively to wash three times, be vacuum dried 24h at 50～70 DEG C, obtain the first product；
5g the first product and 5-10g aniline monomer are added to the solution of DBSA, ultrasonic disperse 65min,
Forming the second product, the mass ratio of described first product and DBSA is 1-1.5: 8-15；
3g Ammonium persulfate. is dissolved in 80-120ml distilled water, is slowly dropped in the second product, stirring reaction 15h, instead
After should terminating, sucking filtration, use distilled water, washing with alcohol product colourless to filtrate respectively, 50～70 DEG C of vacuum drying 24～36h,
To Graphene/hollow ferroso-ferric oxide/polyaniline nano-composite material；
Step 6, by Graphene/hollow ferroso-ferric oxide/polyaniline nano-composite material obtained in step 4, is positioned over paving
It is lined with in the ceramic crucible of potassium permanganate, is placed in Muffle furnace being sintered, first heat up with the heating rate of 10 DEG C/min
To 300 DEG C, it is incubated 30min, then is warming up to 600 DEG C with the heating rate of 12 DEG C/min, be incubated 30min, then with 15 DEG C
The rate of temperature fall of/min is cooled to 500 DEG C, is incubated 20min, is finally warming up to 950 DEG C of insulations with the heating rate of 15 DEG C/min
1-3h, obtains the quality of mesoporous material, described Graphene/hollow ferroso-ferric oxide/polyaniline nano-composite material and potassium permanganate
Ratio is 1: 3-5.
Graphite oxide g described in step 2, dimethyl sulfoxide ml, N-hydroxysuccinimide g and self-control surface conditioning agent g's
Ratio is 0.2-0.5: 20-25: 2-5: 0.1-05, and described self-control surface conditioning agent is by dicyclohexylcarbodiimide, dodecyl
Sodium sulfonate, kayexalate and polyacrylic acid composition, described dicyclohexylcarbodiimide, dodecyl sodium sulfate, polyphenyl
Vinyl sulfonic acid sodium and polyacrylic mass ratio are 1: 1: 2: 3.
The hydrochloric acid solution that concentration is volume ratio 1: 10 of hydrochloric acid in described described step 2.
This Graphene/hollow ferroso-ferric oxide/polyaniline nano-composite material is laminar nano composite wave-suction material, and hollow hemisphere is tied
The ferroferric oxide nano granules homoepitaxial of structure is in two surfaces up and down of redox graphene sheet, a kind of nanometer thickness of formation
The absorbing material of the multi-layer compound structure of degree, loads hollow four ferrum oxide three that particle diameter is about 20-50nm on graphene sheet layer
Grain, and polyaniline-coated is in the graphene sheet layer surface being loaded with hollow Nano ferroso-ferric oxide.
The coupling part weak in graphite after ball milling when graphite is broken up, it is not necessary to through ultrasonic disperse, warp in preparation process
Cross and cold and heat succeed each other and little molecular action, both so that atom is peeled off, reduce energy consumption, and production cycle so that the production cycle
Shorten 5-15h.
The preparation method of the absorbing material of the present invention passes through ferroso-ferric oxide growth in situ on graphene sheet layer and polyaniline exists
The in-situ polymerization on Graphene/ferriferrous oxide composite material surface, thus realize the wave-absorbing effect that material is excellent, at reflection loss
The Absorber Bandwidth of below-10dB is 4.8-5.1GHz；
The hole dimension of described mesoporous material is 5-30nm, and the suction ripple in the range of 1-20Hz is-35-55dB.There is higher electricity
Conductance, the absorbing property in the range of 1-20Hz is excellent, can be used for electromagnetic-wave absorbent, it is also possible to as environment adsorbing materials,
For adsorbing the pollutant such as heavy metal in environment.This mesoporous material electric capacity under the electric current density of 200mA/g is
435-458F/g。。
It is required that applicant uses different heating rates to be warming up to through numerous studies step one of the present invention preparation pre-oxidation graphite
The whipping temp wanted, stirring stage by stage under different whipping temps, and add KMnO the most at different temperature4
Contribute to pre-oxidizing the preparation of graphite so that oxidation is more thoroughly higher than common disposable stirring and adds KMnO4's
10-15%, and the formation of beneficially later stage Graphene；
Step 2 does further surface for graphite oxide process, used homemade surface conditioning agent, by energy after adding
Enough graphite oxide surfaces that enough makes up, for the low shortcoming of metallic iron ion affinity, increase the load capacity of surface Fe ion, also
Making Fe ion below more uniform in the dispersion of graphite surface, the specific surface area of its graphite reaches 35-37m simultaneously2/g；
The graphite processed through sulfonation just has fabulous dissolubility in the later stage, more easily adds to high molecular polymer matrix,
The associativity of the nano composite material formed is more prominent.
During step 5 of the present invention using different heating rates be warming up to required temperature, through the guarantor that once lowers the temperature
Temperature, more contributes to the formation of Graphene/hollow ferroso-ferric oxide so that the absorbing property of the absorbing material ultimately formed is higher,
It is better than performance 5-15% of the absorbing material that commonsense method is formed, and the tri compound absorbing material performance formed is more steady
Fixed；
The present invention in preparation process without use nitrogen or oxygen protection, it is not necessary to hot conditions, it is possible to effectively reduce synthesis
Cost, and effectively raise nano-particle dispersing uniformity in graphite, improve the performance of product.
Detailed description of the invention
Below in conjunction with specific embodiment, the present invention is described in detail.
A kind of mesoporous composite material, it is characterised in that its step is as follows:
Step one, makes graphite a size of 50-200 mesh and obtains graphite powder, add to the hydrochloric acid that mass fraction is 35% molten afterwards
In liquid, stir 30min, use deionized water repeatedly to rinse so that pH value is neutral afterwards, dry stand-by；
By graphite powder, potassium peroxydisulfate and P2O5Adding in concentrated sulphuric acid, form mixture, the pH value of the mixture formed is 1.5,
This mixture is stirred at 60 DEG C 1-2h, then at 80 DEG C, stirs 2-4h, finally with 2 with the ramp of 5 DEG C/min
DEG C/min be warming up to 87 DEG C stirring 1-2h, then use this mixture of distilled water diluting, the pH value of this mixture is diluted to
3.6, place and use after 36h distilled water to filter so that mixture pH value is 6-7, after carry out drying at room temperature, described graphite powder,
Potassium peroxydisulfate, P2O5It is 1-3: 1-2: 1-2: 5-10 with the mass ratio of concentrated sulphuric acid；
Dried mixture is joined stirring 45-60min in concentrated nitric acid so that pH value is 2-4, described dried mixed
Compound is 1-4: 50-100 with the mass ratio of concentrated nitric acid, adds KMnO after stirring at-8 DEG C for the first time4, stir 30min,
At being cooled to-12 DEG C afterwards, second time adds KMnO4, stir 30min, at being finally cooled to-15 DEG C, third time adds
KMnO4, to stir 20min, obtain the graphite mixture of pre-oxidation, described first time adds KMnO4, second time adds KMnO4
KMnO is added with third time4Mass ratio be 1: 2: 3, described dried mixture and total KMnO4Ratio be
1-2∶10-15；
The graphite mixture obtaining pre-oxidation is filtered and dried, is positioned in Muffle furnace and carries out heat treated, the temperature of heat treatment
Degree, for processing 10-20s at 1100 DEG C, processes 15-20s at 1150 DEG C, process 20-30s, obtain expanded graphite at 1180 DEG C；
Step 2, puts into expanded graphite made for step one and is warmed up to 40 DEG C in couveuse, react 3h, subsequently, add with
Consistent amount of first distilled water of graphite mixture volume of pre-oxidation, then reacts 2.5h, by couveuse temperature to 40 DEG C,
Again add after-fractionating water and H2O2Reaction 10-60min, the amount of described after-fractionating water is 1-1.5 times of the first distilled water,
After-fractionating water and H2O2Volume ratio be 4-20: 1, reaction terminate after carry out centrifugation 10min, rotating speed 8000～10000
R/min, centrifugation afterproduct hydrochloric acid solution washs, and the volume of this hydrochloric acid solution is the 10-50 of centrifugation afterproduct volume
Times, finally dialysis obtains graphite oxide in 7-8 days；N-hydroxyl fourth two is added after graphite oxide is used dimethyl sulfoxide ultrasonic dissolution
Acid imide and self-control surface conditioning agent stirs 2h at 35 DEG C, and product carries out sucking filtration, washs, dries, and i.e. obtain surface process
Graphite oxide.
Step 3,
Under room temperature, the graphite oxide obtained in 1g step 2 is joined in the reactor equipped with 500g deionized water, and will reaction
Device is placed in ultrasonic dispersers stirring, stirs 10-15min, uses ammonia regulation aqueous solution to regulate the pH value of system to 11,
And it is warming up to 70 DEG C, then in reactor, add 5-10g sodium borohydride aqueous solution, after keeping sonic oscillation reaction 30～60min,
The temperature of system is down to 15 DEG C, adds 25g p-aminobenzene sulfonic acid, keep sonic oscillation to react 2～4 hours, then stand
React 3 hours, then mixed liquor is carried out sucking filtration to remove solvent, and be washed with deionized more than 2 times, by filtrate weight
Newly it is dispersed in 400～1600g deionized waters, and adds 1～4g hydrazine hydrate, react 12～24 hours at 80 DEG C, product
By sucking filtration, and it is washed with deionized more than 2 times, finally filtrate is dried 24～48 hours and obtains sulfonated graphite；
Step 4, the sulfonated graphite 1-2g obtained by step 3 is carried out at-10-30 DEG C after lyophilization with 1-10g polycyclic oxygen
Ethane-poly(propylene oxide)-poly(ethylene oxide) triblock copolymer is put into ultrasonic disperse in the ethylene glycol of 500ml in the lump and is formed uniformly
First dispersion liquid；Simultaneously by 4-15g by Fecl3·6H2O、Fecl2·4H2O and the mixture of acetyl acetone ferrum composition, 6～25g
Polyvinylpyrrolidone and 10～50g NH4Ac is dissolved in the ethylene glycol of 500-1000mL and forms the second dispersion liquid, by first
Dispersion liquid and the second dispersion liquid mix and blend, and regulate with ammonia, make the settled solution that pH value is 8-10, described
Fecl3·6H2O、Fecl2·4H2The mass ratio of O and acetyl acetone ferrum is 1: 1: 0.5；
Step 5, puts in reactor by the settled solution obtained by 100ml step 3, after sealing, is heated to 150 DEG C,
Insulation 2h, is warming up to 200 DEG C with the heating rate of 2-4 DEG C/min afterwards, is incubated 4h, afterwards with the intensification speed of 3-6 DEG C/min
Rate is warming up to 235 DEG C, is incubated 3h, is then cooled to 200 DEG C of insulation 2h with the cooling rate of 5-7 DEG C/min, the most again with 3-6
DEG C/heating rate of min is warming up to 235 DEG C, it is incubated 7h, after question response completes, reactor is taken out, is allowed to be cooled to room
Temperature, described cooling rate is 3-6 DEG C/min, by the black powder centrifugation 10min of gained, rotating speed 8000～10000r/min,
Use dehydrated alcohol and deionized water respectively to wash three times, be vacuum dried 24h at 50～70 DEG C, obtain the first product；
5g the first product and 5-10g aniline monomer are added to the solution of DBSA, ultrasonic disperse 65min,
Forming the second product, the mass ratio of described first product and DBSA is 1-1.5: 8-15；
3g Ammonium persulfate. is dissolved in 80-120ml distilled water, is slowly dropped in the second product, stirring reaction 15h, instead
After should terminating, sucking filtration, use distilled water, washing with alcohol product colourless to filtrate respectively, 50～70 DEG C of vacuum drying 24～36h,
To Graphene/hollow ferroso-ferric oxide/polyaniline nano-composite material；
Step 6, by Graphene/hollow ferroso-ferric oxide/polyaniline nano-composite material obtained in step 4, is positioned over paving
It is lined with in the ceramic crucible of potassium permanganate, is placed in Muffle furnace being sintered, first heat up with the heating rate of 10 DEG C/min
To 300 DEG C, it is incubated 30min, then is warming up to 600 DEG C with the heating rate of 12 DEG C/min, be incubated 30min, then with 15 DEG C
The rate of temperature fall of/min is cooled to 500 DEG C, is incubated 20min, is finally warming up to 950 DEG C of insulations with the heating rate of 15 DEG C/min
1-3h, obtains the quality of mesoporous material, described Graphene/hollow ferroso-ferric oxide/polyaniline nano-composite material and potassium permanganate
Ratio is 1: 3-5.
Graphite oxide g described in step 2, dimethyl sulfoxide ml, N-hydroxysuccinimide g and self-control surface conditioning agent g's
Ratio is 0.2-0.5: 20-25: 2-5: 0.1-05, and described self-control surface conditioning agent is by dicyclohexylcarbodiimide, dodecyl
Sodium sulfonate, kayexalate and polyacrylic acid composition, described dicyclohexylcarbodiimide, dodecyl sodium sulfate, polyphenyl
Vinyl sulfonic acid sodium and polyacrylic mass ratio are 1: 1: 2: 3.
The hydrochloric acid solution that concentration is volume ratio 1: 10 of hydrochloric acid in described described step 2.
This Graphene/hollow ferroso-ferric oxide/polyaniline nano-composite material is laminar nano composite wave-suction material, and hollow hemisphere is tied
The ferroferric oxide nano granules homoepitaxial of structure is in two surfaces up and down of redox graphene sheet, a kind of nanometer thickness of formation
The absorbing material of the multi-layer compound structure of degree, loads hollow four ferrum oxide three that particle diameter is about 20-50nm on graphene sheet layer
Grain, and polyaniline-coated is in the graphene sheet layer surface being loaded with hollow Nano ferroso-ferric oxide.The hole dimension of described mesoporous material
For 5-30nm, the suction ripple in the range of 1-20Hz is-35-55dB.There is higher electrical conductivity, in the range of 1-20Hz
Absorbing property is excellent, can be used for electromagnetic-wave absorbent, it is also possible to as environment adsorbing materials, for adsorbing the heavy metal in environment
Deng pollutant.This mesoporous material electric capacity under the electric current density of 200mA/g is 435-458F/g.
It should be appreciated that for those of ordinary skills, can be improved according to the above description or be converted, and institute
There are these modifications and variations all should belong to the protection domain of claims of the present invention.
Claims (4)
1. a mesoporous composite material, it is characterised in that the preparation method of this material comprises the following steps:
Step one, makes graphite a size of 50-200 mesh and obtains graphite powder, add to the hydrochloric acid that mass fraction is 35% molten afterwards
In liquid, stir 30min, use deionized water repeatedly to rinse so that pH value is neutral afterwards, dry stand-by；
By graphite powder stand-by for foregoing drying, potassium peroxydisulfate and P2O5Add in concentrated sulphuric acid, form mixture, institute's shape
The pH value of mixture become is 1.5, and this mixture stirs at 60 DEG C 1-2h, then with the ramp of 5 DEG C/min extremely
Stir 2-4h at 80 DEG C, be finally warming up to 87 DEG C of stirring 1-2h with 2 DEG C/min, then use this mixture of distilled water diluting,
The pH value of this mixture is diluted to 3.6, uses distilled water to filter after placing 36h so that mixture pH value is 6-7, after
Carry out drying at room temperature, described graphite powder, potassium peroxydisulfate, P2O5It is 1-3: 1-2: 1-2: 5-10 with the mass ratio of concentrated sulphuric acid；
Dried mixture is joined stirring 45-60min in concentrated nitric acid so that pH value is 2-4, described dried mixed
Compound is 1-4: 50-100 with the mass ratio of concentrated nitric acid, adds KMnO after stirring at-8 DEG C for the first time4, stir 30min,
At being cooled to-12 DEG C afterwards, second time adds KMnO4, stir 30min, at being finally cooled to-15 DEG C, third time adds
KMnO4, to stir 20min, obtain the graphite mixture of pre-oxidation, described first time adds KMnO4, second time adds KMnO4
KMnO is added with third time4Mass ratio be 1: 2: 3, described dried mixture and total KMnO4Ratio be
1-2∶10-15；
The graphite mixture obtaining pre-oxidation is filtered and dried, is positioned in Muffle furnace and carries out heat treated, the temperature of heat treatment
Degree, for processing 10-20s at 1100 DEG C, processes 15-20s at 1150 DEG C, process 20-30s, obtain expanded graphite at 1180 DEG C；
Step 2, puts into expanded graphite made for step one and is warmed up to 40 DEG C in couveuse, react 3h, subsequently, add with
Consistent amount of first distilled water of graphite mixture volume of pre-oxidation, then reacts 2.5h, by couveuse temperature to 40 DEG C,
Again add after-fractionating water and H2O2Reaction 10-60min, the amount of described after-fractionating water is 1-1.5 times of the first distilled water,
After-fractionating water and H2O2Volume ratio be 4-20: 1, reaction terminate after carry out centrifugation 10min, rotating speed 8000～10000
R/min, centrifugation afterproduct hydrochloric acid solution washs, and the volume of this hydrochloric acid solution is the 10-50 of centrifugation afterproduct volume
Times, finally dialysis obtains graphite oxide in 7-8 days；N-hydroxyl fourth two is added after graphite oxide is used dimethyl sulfoxide ultrasonic dissolution
Acid imide and self-control surface conditioning agent stirs 2h at 35 DEG C, and product carries out sucking filtration, washs, dries, and i.e. obtain surface process
Graphite oxide.
Step 3,
Under room temperature, the graphite oxide obtained in 1g step 2 is joined in the reactor equipped with 500g deionized water, and will reaction
Device is placed in ultrasonic dispersers stirring, stirs 10-15min, uses ammonia regulation aqueous solution to regulate the pH value of system to 11,
And it is warming up to 70 DEG C, then in reactor, add 5-10g sodium borohydride aqueous solution, after keeping sonic oscillation reaction 30～60min,
The temperature of system is down to 15 DEG C, adds 25g p-aminobenzene sulfonic acid, keep sonic oscillation to react 2～4 hours, then stand
React 3 hours, then mixed liquor is carried out sucking filtration to remove solvent, and be washed with deionized more than 2 times, by filtrate weight
Newly it is dispersed in 400～1600g deionized waters, and adds 1～4g hydrazine hydrate, react 12～24 hours at 80 DEG C, product
By sucking filtration, and it is washed with deionized more than 2 times, finally filtrate is dried 24～48 hours and obtains sulfonated graphite；
Step 4, the sulfonated graphite 1-2g obtained by step 3 is carried out at-10-30 DEG C after lyophilization with 1-10g polycyclic oxygen
Ethane-poly(propylene oxide)-poly(ethylene oxide) triblock copolymer is put into ultrasonic disperse in the ethylene glycol of 500ml in the lump and is formed uniformly
First dispersion liquid；Simultaneously by 4-15g by Fecl3·6H2O、Fecl2·4H2O and the mixture of acetyl acetone ferrum composition, 6～25g
Polyvinylpyrrolidone and 10～50g NH4Ac is dissolved in the ethylene glycol of 500-1000mL and forms the second dispersion liquid, by first
Dispersion liquid and the second dispersion liquid mix and blend, and regulate with ammonia, make the settled solution that pH value is 8-10, described
Fecl3·6H2O、Fecl2·4H2The mass ratio of O and acetyl acetone ferrum is 1: 1: 0.5；
Step 5, puts in reactor by the settled solution obtained by 100ml step 3, after sealing, is heated to 150 DEG C,
Insulation 2h, is warming up to 200 DEG C with the heating rate of 2-4 DEG C/min afterwards, is incubated 4h, afterwards with the intensification speed of 3-6 DEG C/min
Rate is warming up to 235 DEG C, is incubated 3h, is then cooled to 200 DEG C of insulation 2h with the cooling rate of 5-7 DEG C/min, the most again with 3-6
DEG C/heating rate of min is warming up to 235 DEG C, it is incubated 7h, after question response completes, reactor is taken out, is allowed to be cooled to room
Temperature, described cooling rate is 3-6 DEG C/min, by the black powder centrifugation 10min of gained, rotating speed 8000～10000r/min,
Use dehydrated alcohol and deionized water respectively to wash three times, be vacuum dried 24h at 50～70 DEG C, obtain the first product；
5g the first product and 5-10g aniline monomer are added to the solution of DBSA, ultrasonic disperse 65min,
Forming the second product, the mass ratio of described first product and DBSA is 1-1.5: 8-15；
3g Ammonium persulfate. is dissolved in 80-120ml distilled water, is slowly dropped in the second product, stirring reaction 15h, instead
After should terminating, sucking filtration, use distilled water, washing with alcohol product colourless to filtrate respectively, 50～70 DEG C of vacuum drying 24～36h,
To Graphene/hollow ferroso-ferric oxide/polyaniline nano-composite material；
Step 6, by Graphene/hollow ferroso-ferric oxide/polyaniline nano-composite material obtained in step 4, is positioned over paving
It is lined with in the ceramic crucible of potassium permanganate, is placed in Muffle furnace being sintered, first heat up with the heating rate of 10 DEG C/min
To 300 DEG C, it is incubated 30min, then is warming up to 600 DEG C with the heating rate of 12 DEG C/min, be incubated 30min, then with 15 DEG C
The rate of temperature fall of/min is cooled to 500 DEG C, is incubated 20min, is finally warming up to 950 DEG C of insulations with the heating rate of 15 DEG C/min
1-3h, obtains the quality of mesoporous material, described Graphene/hollow ferroso-ferric oxide/polyaniline nano-composite material and potassium permanganate
Ratio is 1: 3-5.
Preparation method the most according to claim 1, it is characterised in that graphite oxide g described in step 2, diformazan are sub-
The ratio of sulfone ml, N-hydroxysuccinimide g and self-control surface conditioning agent g is 0.2-0.5: 20-25: 2-5: 0.1-05,
Described self-control surface conditioning agent is by dicyclohexylcarbodiimide, dodecyl sodium sulfate, kayexalate and polyacrylic acid group
Becoming, described dicyclohexylcarbodiimide, dodecyl sodium sulfate, kayexalate and polyacrylic mass ratio are
1∶1∶2∶3。
Preparation method the most according to claim 1, it is characterised in that in described described step 2, the concentration of hydrochloric acid is
The hydrochloric acid solution of volume ratio 1: 10.
Nano combined absorbing material the most according to claim 1, it is characterised in that this Graphene/hollow ferroso-ferric oxide
/ polyaniline nano-composite material is laminar nano composite wave-suction material, and the ferroferric oxide nano granules of hollow hemisphere structure is uniform
It is grown in two surfaces up and down of redox graphene sheet, the suction ripple material of the multi-layer compound structure of a kind of nano thickness of formation
Material, loads hollow four ferrum oxide three granules that particle diameter is about 20-50nm on graphene sheet layer, and polyaniline-coated is in being loaded with
The graphene sheet layer surface of hollow Nano ferroso-ferric oxide.
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