CN105880618A - Preparation method for composite mesoporous material with nano nickel loaded on graphene - Google Patents
Preparation method for composite mesoporous material with nano nickel loaded on graphene Download PDFInfo
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- CN105880618A CN105880618A CN201510017384.2A CN201510017384A CN105880618A CN 105880618 A CN105880618 A CN 105880618A CN 201510017384 A CN201510017384 A CN 201510017384A CN 105880618 A CN105880618 A CN 105880618A
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 75
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title claims abstract description 29
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 21
- 239000013335 mesoporous material Substances 0.000 title claims abstract description 15
- 239000002131 composite material Substances 0.000 title abstract description 4
- 229910002804 graphite Inorganic materials 0.000 claims abstract description 44
- 239000010439 graphite Substances 0.000 claims abstract description 44
- 239000011358 absorbing material Substances 0.000 claims abstract description 24
- 238000000034 method Methods 0.000 claims abstract description 13
- 229920000767 polyaniline Polymers 0.000 claims abstract description 5
- 239000000203 mixture Substances 0.000 claims description 38
- 238000003756 stirring Methods 0.000 claims description 33
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 30
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 24
- 238000010792 warming Methods 0.000 claims description 23
- 239000012286 potassium permanganate Substances 0.000 claims description 22
- 239000000047 product Substances 0.000 claims description 22
- 239000007788 liquid Substances 0.000 claims description 21
- 239000006185 dispersion Substances 0.000 claims description 20
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 18
- 239000012153 distilled water Substances 0.000 claims description 18
- 238000010438 heat treatment Methods 0.000 claims description 17
- 239000002245 particle Substances 0.000 claims description 17
- 230000003647 oxidation Effects 0.000 claims description 14
- 238000007254 oxidation reaction Methods 0.000 claims description 14
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 12
- 238000005119 centrifugation Methods 0.000 claims description 12
- 238000009413 insulation Methods 0.000 claims description 12
- -1 poly(propylene oxide) Polymers 0.000 claims description 12
- 239000001117 sulphuric acid Substances 0.000 claims description 12
- 235000011149 sulphuric acid Nutrition 0.000 claims description 12
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 10
- 239000003795 chemical substances by application Substances 0.000 claims description 10
- 238000006243 chemical reaction Methods 0.000 claims description 9
- 230000003750 conditioning effect Effects 0.000 claims description 7
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 6
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims description 6
- QOSSAOTZNIDXMA-UHFFFAOYSA-N Dicylcohexylcarbodiimide Chemical group C1CCCCC1N=C=NC1CCCCC1 QOSSAOTZNIDXMA-UHFFFAOYSA-N 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- NQTADLQHYWFPDB-UHFFFAOYSA-N N-Hydroxysuccinimide Chemical compound ON1C(=O)CCC1=O NQTADLQHYWFPDB-UHFFFAOYSA-N 0.000 claims description 6
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 6
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 6
- 239000011363 dried mixture Substances 0.000 claims description 6
- 238000001914 filtration Methods 0.000 claims description 6
- 229910017604 nitric acid Inorganic materials 0.000 claims description 6
- 229920002401 polyacrylamide Polymers 0.000 claims description 6
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 6
- 235000019394 potassium persulphate Nutrition 0.000 claims description 6
- 238000000746 purification Methods 0.000 claims description 6
- 150000001875 compounds Chemical class 0.000 claims description 5
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical group [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 claims description 4
- 229940059939 kayexalate Drugs 0.000 claims description 4
- 230000001590 oxidative effect Effects 0.000 claims description 4
- 229920001467 poly(styrenesulfonates) Chemical group 0.000 claims description 4
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 3
- 229920002125 Sokalan® Chemical group 0.000 claims description 3
- JCYCCXPTYNHDRV-UHFFFAOYSA-N [Ni].OCCO Chemical compound [Ni].OCCO JCYCCXPTYNHDRV-UHFFFAOYSA-N 0.000 claims description 3
- 229910021529 ammonia Inorganic materials 0.000 claims description 3
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 3
- 239000000919 ceramic Substances 0.000 claims description 3
- 230000009514 concussion Effects 0.000 claims description 3
- 229960000935 dehydrated alcohol Drugs 0.000 claims description 3
- 239000008367 deionised water Substances 0.000 claims description 3
- 229910021641 deionized water Inorganic materials 0.000 claims description 3
- 238000000502 dialysis Methods 0.000 claims description 3
- 238000007865 diluting Methods 0.000 claims description 3
- 238000004090 dissolution Methods 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- 239000000706 filtrate Substances 0.000 claims description 3
- 238000004108 freeze drying Methods 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 239000000178 monomer Substances 0.000 claims description 3
- 239000004584 polyacrylic acid Chemical group 0.000 claims description 3
- 125000003367 polycyclic group Chemical group 0.000 claims description 3
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 3
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 3
- 239000000843 powder Substances 0.000 claims description 3
- 238000007789 sealing Methods 0.000 claims description 3
- 229920000428 triblock copolymer Polymers 0.000 claims description 3
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 3
- 238000001291 vacuum drying Methods 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- 229910052799 carbon Inorganic materials 0.000 claims 1
- 150000003457 sulfones Chemical class 0.000 claims 1
- 229910001453 nickel ion Inorganic materials 0.000 abstract description 9
- 239000000463 material Substances 0.000 abstract description 7
- 238000003763 carbonization Methods 0.000 abstract 1
- 230000015572 biosynthetic process Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000010410 layer Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 241000446313 Lamella Species 0.000 description 2
- 230000006378 damage Effects 0.000 description 2
- 201000010099 disease Diseases 0.000 description 2
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000002114 nanocomposite Substances 0.000 description 2
- 229920006389 polyphenyl polymer Polymers 0.000 description 2
- 230000005855 radiation Effects 0.000 description 2
- DAJSVUQLFFJUSX-UHFFFAOYSA-M sodium;dodecane-1-sulfonate Chemical compound [Na+].CCCCCCCCCCCCS([O-])(=O)=O DAJSVUQLFFJUSX-UHFFFAOYSA-M 0.000 description 2
- BWYYYTVSBPRQCN-UHFFFAOYSA-M sodium;ethenesulfonate Chemical compound [Na+].[O-]S(=O)(=O)C=C BWYYYTVSBPRQCN-UHFFFAOYSA-M 0.000 description 2
- 206010028980 Neoplasm Diseases 0.000 description 1
- 230000002745 absorbent Effects 0.000 description 1
- 239000002250 absorbent Substances 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000017531 blood circulation Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 230000005672 electromagnetic field Effects 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 210000000987 immune system Anatomy 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 230000005389 magnetism Effects 0.000 description 1
- 230000005415 magnetization Effects 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 210000000653 nervous system Anatomy 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 210000000056 organ Anatomy 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
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- 125000006850 spacer group Chemical group 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
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- Carbon And Carbon Compounds (AREA)
Abstract
The invention discloses a preparation method for a composite mesoporous material with nano nickel loaded on graphene. The preparation method comprises the steps that graphite oxide is prepared; nano-nickel ions are uniformly grown on a graphene slice layer; then a wave absorbing material is prepared by enabling the graphene slice layer surface loaded with the nano-nickel ions to be coated with polyaniline; and finally the mesoporous material is prepared through high-temperature carbonization treatment. According to the preparation method for the composite mesoporous material with the nano nickel loaded on the graphene, the method is convenient and efficient, and the material can be used as an electromagnetic wave absorbing material and an environment adsorbing material.
Description
Technical field
The present invention relates to absorbing material field, the preparation side of a kind of graphene-supported nano nickel complex mesoporous material
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 combined
The preparation method of mesoporous material.
Technical scheme is as follows:
The preparation method of a kind of graphene-supported nano nickel complex mesoporous material, it is characterised in that its step is as follows:
Step one, the preparation of pre-oxidation graphite
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。
Step 2, the preparation of the graphite oxide that surface processes
The graphite mixture of pre-oxidation made for step one is put into couveuse is warmed up to 40 DEG C, react 3h, subsequently, add
With consistent amount of first distilled water of graphite mixture volume of pre-oxidation, then react 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 the 1-1.5 of the first distilled water
Times, after-fractionating water and H2O2Volume ratio be 4-20: 1, reaction terminate after carry out centrifugation 10min, rotating speed 9500r/min,
Centrifugation afterproduct hydrochloric acid solution washs, and the volume of this hydrochloric acid solution is 10-50 times of centrifugation afterproduct volume,
Rear dialysis obtains graphite oxide in 7-8 days,
Graphite oxide is put into purification liquid and prepares mixing liquid, the graphite oxide after carrying out concussion dispersion and being filtrated to get to purify,
Described purification liquid is due to the concentrated sulphuric acid of 1.72g/ml and H2O2Composition, concentrated sulphuric acid and H2O2Mass ratio be 1-2: 2-5,；
Graphite oxide after purifying adds N-hydroxysuccinimide and self-control surface after using dimethyl sulfoxide ultrasonic dissolution
2h stir in reason agent at 35 DEG C, and product carries out sucking filtration, washs, dries, and i.e. obtains the graphite oxide of surface process；
Step 3, dispersion
The graphite oxide 1-2g that surface obtained by step 2 processes is carried out at-10-30 DEG C after lyophilization with 1-10g polycyclic
Oxidative ethane-poly(propylene oxide)-poly(ethylene oxide) triblock copolymer and 1g are made up of polymethylacrylic acid and polyacrylamide
Mixture (mass ratio of polymethylacrylic acid and polyacrylamide is 1: 1) put in the lump the ethylene glycol of 500ml is carried out ultrasonic
Dispersion, then radiates 36h under ultraviolet irradiation and forms 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 4, 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 5, by absorbing material obtained in step 4, being positioned over place mat has in the ceramic crucible of potassium permanganate,
It is placed in Muffle furnace being sintered, is first warming up to 300 DEG C with the heating rate of 10 DEG C/min, insulation 30min, then with
The heating rate of 12 DEG C/min is warming up to 600 DEG C, is incubated 30min, is then cooled to 500 with the rate of temperature fall of 15 DEG C/min
DEG C, it is incubated 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, institute
The mass ratio stating absorbing material and potassium permanganate is 1: 3-5.
The particle diameter of described graphite powder is 15-30um.
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；
Dispersion effect in step 3 is good, and stability is high, be conducive to next step operation and with the combination of nickel ion；
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；
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 complex mesoporous material, it is characterised in that its step is as follows:
Step one, the preparation of pre-oxidation graphite
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。
Step 2, the preparation of the graphite oxide that surface processes
The graphite mixture of pre-oxidation made for step one is put into couveuse is warmed up to 40 DEG C, react 3h, subsequently, add
With consistent amount of first distilled water of graphite mixture volume of pre-oxidation, then react 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 the 1-1.5 of the first distilled water
Times, after-fractionating water and H2O2Volume ratio be 4-20: 1, reaction terminate after carry out centrifugation 10min, rotating speed 9500r/min,
Centrifugation afterproduct hydrochloric acid solution washs, and the volume of this hydrochloric acid solution is 10-50 times of centrifugation afterproduct volume,
Rear dialysis obtains graphite oxide in 7-8 days,
Graphite oxide is put into purification liquid and prepares mixing liquid, the graphite oxide after carrying out concussion dispersion and being filtrated to get to purify,
Described purification liquid is due to the concentrated sulphuric acid of 1.72g/ml and H2O2Composition, concentrated sulphuric acid and H2O2Mass ratio be 1-2: 2-5,；
Graphite oxide after purifying adds N-hydroxysuccinimide and self-control surface after using dimethyl sulfoxide ultrasonic dissolution
2h stir in reason agent at 35 DEG C, and product carries out sucking filtration, washs, dries, and i.e. obtains the graphite oxide of surface process；
Step 3, dispersion
The graphite oxide 1-2g that surface obtained by step 2 processes is carried out at-10-30 DEG C after lyophilization with 1-10g polycyclic
Oxidative ethane-poly(propylene oxide)-poly(ethylene oxide) triblock copolymer and 1g are made up of polymethylacrylic acid and polyacrylamide
Mixture (mass ratio of polymethylacrylic acid and polyacrylamide is 1: 1) put in the lump the ethylene glycol of 500ml is carried out ultrasonic
Dispersion, then radiates 36h under ultraviolet irradiation and forms 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 4, 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 5, by absorbing material obtained in step 4, being positioned over place mat has in the ceramic crucible of potassium permanganate,
It is placed in Muffle furnace being sintered, is first warming up to 300 DEG C with the heating rate of 10 DEG C/min, insulation 30min, then with
The heating rate of 12 DEG C/min is warming up to 600 DEG C, is incubated 30min, is then cooled to 500 with the rate of temperature fall of 15 DEG C/min
DEG C, it is incubated 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, institute
The mass ratio stating absorbing material and potassium permanganate is 1: 3-5.
The particle diameter of described graphite powder is 15-30um.
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.
Claims (5)
1. the preparation method of a graphene-supported nano nickel complex mesoporous material, it is characterised in that its step is as follows:
Step one, the preparation of pre-oxidation graphite
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。
Step 2, the preparation of the graphite oxide that surface processes
The graphite mixture of pre-oxidation made for step one is put into couveuse is warmed up to 40 DEG C, react 3h, subsequently, add
With consistent amount of first distilled water of graphite mixture volume of pre-oxidation, then react 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 the 1-1.5 of the first distilled water
Times, after-fractionating water and H2O2Volume ratio be 4-20: 1, reaction terminate after carry out centrifugation 10min, rotating speed 9500r/min,
Centrifugation afterproduct hydrochloric acid solution washs, and the volume of this hydrochloric acid solution is 10-50 times of centrifugation afterproduct volume,
Rear dialysis obtains graphite oxide in 7-8 days,
Graphite oxide is put into purification liquid and prepares mixing liquid, the graphite oxide after carrying out concussion dispersion and being filtrated to get to purify,
Described purification liquid is due to the concentrated sulphuric acid of 1.72g/ml and H2O2Composition, concentrated sulphuric acid and H2O2Mass ratio be 1-2: 2-5,；
Graphite oxide after purifying adds N-hydroxysuccinimide and self-control surface after using dimethyl sulfoxide ultrasonic dissolution
2h stir in reason agent at 35 DEG C, and product carries out sucking filtration, washs, dries, and i.e. obtains the graphite oxide of surface process；
Step 3, dispersion
The graphite oxide 1-2g that surface obtained by step 2 processes is carried out at-10-30 DEG C after lyophilization with 1-10g polycyclic
Oxidative ethane-poly(propylene oxide)-poly(ethylene oxide) triblock copolymer and 1g are made up of polymethylacrylic acid and polyacrylamide
Mixture (mass ratio of polymethylacrylic acid and polyacrylamide is 1: 1) put in the lump the ethylene glycol of 500ml is carried out ultrasonic
Dispersion, then radiates 36h under ultraviolet irradiation and forms 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 4, 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 5, by absorbing material obtained in step 4, 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 the particle diameter of described graphite powder is 15-30um.
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.
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| CN102604593A (en) * | 2012-03-16 | 2012-07-25 | 北京师范大学 | Cubic-phase nickel nanostructure-graphene complex and preparation method thereof |
| CN103044915A (en) * | 2013-01-17 | 2013-04-17 | 黑龙江大学 | Preparation method of polyaniline/graphene/nano nickel composite material |
| CN103311428A (en) * | 2013-06-14 | 2013-09-18 | 哈尔滨工业大学 | Method for manufacturing graphene/polyaniline thermoelectric thin film |
| CN103641488A (en) * | 2013-12-03 | 2014-03-19 | 南昌航空大学 | Method for preparing graphene doped polyaniline-based carbon coated nickel zinc ferrite mesoporous material |
| US20140158944A1 (en) * | 2012-12-11 | 2014-06-12 | National Tsing Hua University | Polyaniline composites and fabrication method thereof |
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| CN102604593A (en) * | 2012-03-16 | 2012-07-25 | 北京师范大学 | Cubic-phase nickel nanostructure-graphene complex and preparation method thereof |
| US20140158944A1 (en) * | 2012-12-11 | 2014-06-12 | National Tsing Hua University | Polyaniline composites and fabrication method thereof |
| CN103044915A (en) * | 2013-01-17 | 2013-04-17 | 黑龙江大学 | Preparation method of polyaniline/graphene/nano nickel composite material |
| CN103311428A (en) * | 2013-06-14 | 2013-09-18 | 哈尔滨工业大学 | Method for manufacturing graphene/polyaniline thermoelectric thin film |
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