CN105880620A - Preparation method for graphene and loaded nano-nickel compounded mesoporous material - Google Patents
Preparation method for graphene and loaded nano-nickel compounded mesoporous material Download PDFInfo
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Abstract
The invention discloses a preparation method for a graphene and loaded nano-nickel compounded mesoporous material. The preparation method includes the steps that graphite oxide is prepared; and nano-nickel particles are evenly grown on a graphene flaky layer, then polyaniline is wrapped and loaded on the surface of the graphene flaky layer to obtain a wave absorption material, and finally the mesoporous material is obtained through high-temperature carbonization treatment. The preparation method for the graphene and loaded nano-nickel compounded mesoporous material is convenient and rapid to operate, and the material can serve as not only a magnetic wave absorption material but also an environmental absorption material.
Description
Technical field
The present invention relates to absorbing material field, the system of a kind of graphene-supported nano nickel mesoporous composite material
Preparation Method.
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, loads nano nickel ion at graphenic surface, is possible not only to improve magnetism of material energy, strengthens compound
The impedance matching of the magnetic loss of material, beneficially composite, and nano nickel ion particles reduces Graphene as spacer medium
Dry run stacks again in three-dimensional graphite structure, stable graphene film Rotating fields is played considerable effect.
The technical problem to be solved is for the deficiencies in the prior art, it is provided that a kind of graphene-supported nano nickel is mesoporous
The preparation method of composite.
Technical scheme is as follows:
The preparation method of a kind of graphene-supported nano nickel 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, joins the graphite oxide obtained in 1g step 2 in the reactor equipped with 500g deionized water under room temperature,
And reactor is placed in ultrasonic dispersers stirring, stir 10-15min, use ammonia regulation aqueous solution to be adjusted by the pH value of system
Joint is to 11, and is warming up to 70 DEG C, then adds 5-10g sodium borohydride aqueous solution in reactor, keeps sonic oscillation reaction
After 30～60min, the temperature of system is down to 15 DEG C, adds 25g p-aminobenzene sulfonic acid, keep sonic oscillation reaction 2～4
Hour, then standing and reacting 3 hours, then mixed liquor is carried out sucking filtration to remove solvent, and be washed with deionized more than 2 times,
Filtrate is dispersed in again in 400～1600g deionized waters, and adds 1～4g hydrazine hydrate, at 80 DEG C, react 12～24
Hour, product passes through sucking filtration, and is washed with deionized more than 2 times, finally filtrate is dried 24～48 hours and obtains sulfonation
Graphite；
Step 4, dispersion
Sulfonated graphite 1-2g obtained by step 3 is carried out at-10-30 DEG C after lyophilization with 1-10g poly(ethylene oxide)-polycyclic
Ethylene Oxide-poly(ethylene oxide) triblock copolymer is put into ultrasonic disperse in the ethylene glycol of 500ml in the lump and is formed uniform first dispersion
Liquid；Simultaneously by 20-40ml protochloride nickel ethylene glycol solution (0.1mol/ml), 6～25g polyvinylpyrrolidones and 10～50g
NH4Ac is dissolved in the ethylene glycol of 500-1000mL and forms the second dispersion liquid, the first dispersion liquid and the second dispersion liquid is mixed and stirs
Mix, and regulate with ammonia, make the settled solution that pH value is 9-11；
Step 5, puts in reactor by the settled solution obtained by 100ml step 3, after sealing, is heated to 130 DEG C,
Insulation 2h, is warming up to 150 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 200 DEG C, is incubated 3h, is then cooled to 180 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 200 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 powder centrifugation 10min of gained, rotating speed 8000～10000r/min, adopts
Respectively wash three times with dehydrated alcohol and deionized water, 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 absorbing material.
Step 6, by absorbing material obtained in step 5, being positioned over place mat has in the ceramic crucible of potassium permanganate, is placed in
Muffle furnace is sintered, is first warming up to 300 DEG C with the heating rate of 10 DEG C/min, be incubated 30min, then with 12 DEG C/min
Heating rate be warming up to 600 DEG C, be incubated 30min, be then cooled to 500 DEG C with the rate of temperature fall of 15 DEG C/min, insulation
20min, is finally warming up to 950 DEG C of insulation 1-3h with the heating rate of 15 DEG C/min, obtains mesoporous material, described absorbing material
It is 1: 3-5 with the mass ratio of potassium permanganate.
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 absorbing material is laminar nano composite wave-suction material, and nano nickel uniform particle is grown in graphene sheet layer, at Graphene
Load the nano nickel particle that particle diameter is about 20-100nm on lamella, and polyaniline-coated is in the Graphene being loaded with nano nickel particle
Sheet surfaces.
With chemical bonds between Graphene and nano nickel ion in absorbing material obtained by the present invention, in conjunction with very tight, will not
Because the stirring in later stage etc. make to depart from, chemical property is also stable, and polyaniline-coated is in the graphene film being loaded with nano nickel particle
Layer surface protection nickel ion is not oxidized, and the saturation magnetization of absorbing material of the present invention is 15.7-38.5emu/g.
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
425-443F/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 metal ion affinity, increase the load capacity of surface nickel ion, also simultaneously
Making nickel ion below more uniform in the dispersion of graphite surface, the specific surface area of its graphite reaches 35-37m2/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 4 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-supported nano nickel absorbing material so that the absorbing property of the absorbing material ultimately formed is more
By force, 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
Stable；
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；
The electrical conductivity of the present invention graphene-supported nano nickel absorbing material: 4.17*10-3-8.27*10-3S/cm, saturation magnetization
For 15.7-38.5emu/g.
Detailed description of the invention
Below in conjunction with specific embodiment, the present invention is described in detail.
The preparation method of a kind of graphene-supported nano nickel 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 monohydroxy 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, joins the graphite oxide obtained in 1g step 2 in the reactor equipped with 500g deionized water under room temperature,
And reactor is placed in ultrasonic dispersers stirring, stir 10-15min, use ammonia regulation aqueous solution to be adjusted by the pH value of system
Joint is to 11, and is warming up to 70 DEG C, then adds 5-10g sodium borohydride aqueous solution in reactor, keeps sonic oscillation reaction
After 30～60min, the temperature of system is down to 15 DEG C, adds 25g p-aminobenzene sulfonic acid, keep sonic oscillation reaction 2～4
Hour, then standing and reacting 3 hours, then mixed liquor is carried out sucking filtration to remove solvent, and be washed with deionized more than 2 times,
Filtrate is dispersed in again in 400～1600g deionized waters, and adds 1～4g hydrazine hydrate, at 80 DEG C, react 12～24
Hour, product passes through sucking filtration, and is washed with deionized more than 2 times, finally filtrate is dried 24～48 hours and obtains sulfonation
Graphite；
Step 4, dispersion
Sulfonated graphite 1-2g obtained by step 3 is carried out at-10-30 DEG C after lyophilization with 1-10g poly(ethylene oxide)-polycyclic
Ethylene Oxide-poly(ethylene oxide) triblock copolymer is put into ultrasonic disperse in the ethylene glycol of 500ml in the lump and is formed uniform first dispersion
Liquid；Simultaneously by 20-40ml protochloride nickel ethylene glycol solution (0.1mol/ml), 6～25g polyvinylpyrrolidones and 10～50g
NH4Ac is dissolved in the ethylene glycol of 500-1000mL and forms the second dispersion liquid, the first dispersion liquid and the second dispersion liquid is mixed and stirs
Mix, and regulate with ammonia, make the settled solution that pH value is 9-11；
Step 5, puts in reactor by the settled solution obtained by 100ml step 3, after sealing, is heated to 130 DEG C,
Insulation 2h, is warming up to 150 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 200 DEG C, is incubated 3h, is then cooled to 180 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 200 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 powder centrifugation 10min of gained, rotating speed 8000～10000r/min, adopts
Respectively wash three times with dehydrated alcohol and deionized water, 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 absorbing material.
Step 6, by absorbing material obtained in step 5, being positioned over place mat has in the ceramic crucible of potassium permanganate, is placed in
Muffle furnace is sintered, is first warming up to 300 DEG C with the heating rate of 10 DEG C/min, be incubated 30min, then with 12 DEG C/min
Heating rate be warming up to 600 DEG C, be incubated 30min, be then cooled to 500 DEG C with the rate of temperature fall of 15 DEG C/min, insulation
20min, is finally warming up to 950 DEG C of insulation 1-3h with the heating rate of 15 DEG C/min, obtains mesoporous material, described absorbing material
It is 1: 3-5 with the mass ratio of potassium permanganate.
Graphite oxide g described in step 2, dimethyl sulfoxide ml, N monohydroxy succimide 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 absorbing material is laminar nano composite wave-suction material, and nano nickel uniform particle is grown in graphene sheet layer, at Graphene
Load the nano nickel particle that particle diameter is about 20-100nm on lamella, and polyaniline-coated is in the Graphene being loaded with nano nickel particle
Sheet surfaces.Prepared thickness be the reflection loss peak of the absorbing material sample of 2mm be 21.9dB, reflection loss-10dB with
Under Absorber Bandwidth be up to 4.6GHz, it is possible to effectively absorb the electromagnetic wave of this frequency range.The hole dimension of described mesoporous material is
5-30nm, the suction ripple in the range of 1-20Hz is-35-55dB.There is higher electrical conductivity, the suction ripple in the range of 1-20Hz
Excellent performance, can be used for electromagnetic-wave absorbent, it is also possible to as environment adsorbing materials, for adsorbing the dirts such as heavy metal in environment
Dye thing.This mesoporous material electric capacity under the electric current density of 200mA/g is 425-443F/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. the preparation method of a graphene-supported nano nickel 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 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, joins the graphite oxide obtained in 1g step 2 in the reactor equipped with 500g deionized water under room temperature,
And reactor is placed in ultrasonic dispersers stirring, stir 10-15min, use ammonia regulation aqueous solution to be adjusted by the pH value of system
Joint is to 11, and is warming up to 70 DEG C, then adds 5-10g sodium borohydride aqueous solution in reactor, keeps sonic oscillation reaction
After 30～60min, the temperature of system is down to 15 DEG C, adds 25g p-aminobenzene sulfonic acid, keep sonic oscillation reaction 2～4
Hour, then standing and reacting 3 hours, then mixed liquor is carried out sucking filtration to remove solvent, and be washed with deionized more than 2 times,
Filtrate is dispersed in again in 400～1600g deionized waters, and adds 1～4g hydrazine hydrate, at 80 DEG C, react 12～24
Hour, product passes through sucking filtration, and is washed with deionized more than 2 times, finally filtrate is dried 24～48 hours and obtains sulfonation
Graphite；
Step 4, dispersion
Sulfonated graphite 1-2g obtained by step 3 is carried out at-10-30 DEG C after lyophilization with 1-10g poly(ethylene oxide)-polycyclic
Ethylene Oxide-poly(ethylene oxide) triblock copolymer is put into ultrasonic disperse in the ethylene glycol of 500ml in the lump and is formed uniform first dispersion
Liquid；Simultaneously by 20-40ml protochloride nickel ethylene glycol solution (0.1mol/ml), 6～25g polyvinylpyrrolidones and 10～50g
NH4Ac is dissolved in the ethylene glycol of 500-1000mL and forms the second dispersion liquid, the first dispersion liquid and the second dispersion liquid is mixed and stirs
Mix, and regulate with ammonia, make the settled solution that pH value is 9-11；
Step 5, puts in reactor by the settled solution obtained by 100ml step 3, after sealing, is heated to 130 DEG C,
Insulation 2h, is warming up to 150 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 200 DEG C, is incubated 3h, is then cooled to 180 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 200 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 powder centrifugation 10min of gained, rotating speed 8000～10000r/min, adopts
Respectively wash three times with dehydrated alcohol and deionized water, 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 absorbing material.
Step 6, by absorbing material obtained in step 5, being positioned over place mat has in the ceramic crucible of potassium permanganate, is placed in
Muffle furnace is sintered, is first warming up to 300 DEG C with the heating rate of 10 DEG C/min, be incubated 30min, then with 12 DEG C/min
Heating rate be warming up to 600 DEG C, be incubated 30min, be then cooled to 500 DEG C with the rate of temperature fall of 15 DEG C/min, insulation
20min, is finally warming up to 950 DEG C of insulation 1-3h with the heating rate of 15 DEG C/min, obtains mesoporous material, described absorbing material
It is 1: 3-5 with the mass ratio of potassium permanganate.
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 absorbing material is that laminar nano is multiple
Closing absorbing material, nano nickel uniform particle is grown in graphene sheet layer, loads particle diameter and be about 20-100nm on graphene sheet layer
Nano nickel particle, and polyaniline-coated is in the graphene sheet layer surface being loaded with nano nickel particle.
Priority Applications (1)
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