CN108726514A - porous graphene material and preparation method thereof - Google Patents
porous graphene material and preparation method thereof Download PDFInfo
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- CN108726514A CN108726514A CN201710258245.8A CN201710258245A CN108726514A CN 108726514 A CN108726514 A CN 108726514A CN 201710258245 A CN201710258245 A CN 201710258245A CN 108726514 A CN108726514 A CN 108726514A
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- C01—INORGANIC CHEMISTRY
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- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
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- C01—INORGANIC CHEMISTRY
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- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/16—Pore diameter
Abstract
The present invention relates to field of material technology, and in particular to porous graphene material and preparation method thereof.Technical problem to be solved by the invention is to provide a kind of preparation methods of porous graphene material, include the following steps：A, graphite oxide powder is dispersed in water by ultrasound stripping, obtains graphene oxide water solution；The compound of metal ion is dissolved in water, the compound water solution of metal ion is obtained；B, by two kinds of solution mixings of step a, liquid is removed, solid is obtained；C, under an inert gas, solid is warming up to 600~1000 DEG C of 1~4h of heat preservation；D, acid handles, is washed till neutrality, is drying to obtain porous graphene material.The method of the present invention can obtain the controllable porous graphene material of porosity and aperture, to meet different requirements by adjusting the addition and heat treatment temperature of graphite oxide powder and the compound of metal ion.
Description
Technical field
The present invention relates to field of material technology, and in particular to a kind of porous graphene material and preparation method thereof.
Background technology
As the graphene that carbon family attracts attention, because of its unique two-dimensional structure and excellent electricity, mechanics, light
, calorifics, magnetic property have broad application prospects in fields such as electronics, information, the energy, material and biological medicines.Especially exist
Energy storage material field, huge specific surface area and good electric conductivity make it can be used as energy storage material lithium-ion electric of new generation
The electrode material of pond, ultracapacitor, fuel cell etc..But the band gap of intrinsic graphene is zero, shows as Half-metallic,
Device made of graphene is caused not have switching behaviour.Simultaneously as having stronger Van der Waals force between graphene sheet layer
It interacts with π-π, easily reuniting stacks, and causes the specific surface area of graphene in actual use to become smaller, the phenomenon that Close stack
The transfers of substance are hindered, these significantly limit its answering in terms of energy storage material and electronics, opto-electronic device
With.
Porous graphene refers to the carbon material with hole on graphene basal plane, also has researcher that three-dimensional is assembled into hole
Graphene be known as porous graphene, but since itself does not have intrinsic pore structure, not patent of the present invention discuss range it
It is interior.A large amount of theoretical calculation and the experimental results showed that, by introducing hole on graphene basal plane, band gap can be opened, from
And Effective Regulation its electricity, mechanics, optically and thermally performance, while the channel of mass transfer in graphene is also got through, has allowed object
Mass-energy conveniently and efficiently carries out two-dimentional basal plane and the transmission in axial direction and conduction in graphene.The preparation of porous graphene at present
Method mainly has photoetching process, chemical vapour deposition technique, soda acid etching method, thermal redox method etc..Wherein photoetching process, chemical gaseous phase
Although sedimentation can obtain the porous graphene of high quality, these method manufacturing costs are higher, low yield；Soda acid is carved
Erosion method needs to use strong acid and strong base, though preparation process is fairly simple, but has certain operational hazards, and to the anti-corruption of equipment
Corrosion proposes more requirements.And thermal redox method needs to use the drug of the strong oxidizing properties such as potassium permanganate.These are lacked
Point greatly limits the preparation and application of porous graphene material.Therefore, explore design it is a kind of safe and reliable, can be big
Prepared by scale and simple and practicable method is particularly important to prepare porous graphene material.
Invention content
For the existing method for preparing porous graphene, there are the dangerous medicines such as of high cost, low yield and use highly basic strong acid
The shortcomings of product, the present invention provides a kind of new methods for preparing porous graphene material.This method has easy to operate, safety
The advantages of；And the porous graphene material has many advantages, such as aperture, controlled porosity.
Technical problem to be solved by the invention is to provide a kind of preparation methods of porous graphene material.This method includes
Following steps：
A, graphite oxide powder is dispersed in water by ultrasound stripping, obtains graphene oxide water solution；Metal will be contained
The compound of ion is dissolved in water, and obtains the compound water solution of metal ion；
B, by two kinds of solution mixings of step a, liquid is removed, solid is obtained；
C, under an inert gas, solid is warming up to 600~1000 DEG C of 1~4h of heat preservation；
D, acid handles, is washed till neutrality, is drying to obtain porous graphene material.
Preferably, in the preparation method step a of above-mentioned porous graphene material, the ultrasonic time is 30~120min,
Ultrasonic power is 150~600W.
Preferably, in the preparation method step a of above-mentioned porous graphene material, the concentration of the graphene oxide water solution
For 1~8mg/mL.
Preferably, in the preparation method step a of above-mentioned porous graphene material, the compound water-soluble of the metal ion
A concentration of 1~8mg/mL of liquid.
Preferably, in the preparation method step a of above-mentioned porous graphene material, the compound of the metal ion is water
Dissolubility, and when the metal ion is converted into corresponding oxide, which can react with diluted acid.
Further, in the preparation method step a of above-mentioned porous graphene material, the compound of the metal ion is
Water soluble compound, water soluble compound with manganese ions containing ferric ion, the water soluble compound containing zinc ion contain
At least one of water soluble compound of copper ion.
Further, in the preparation method step a of above-mentioned porous graphene material, the compound of the metal ion
Anion be chlorion, sulfate ion, nitrate ion or acetate ion in any one.
Preferably, in the preparation method step b of above-mentioned porous graphene material, the mixing uses ultrasonic power, ultrasound
Time is 30~120min, and ultrasonic power is 150~600W.
Preferably, in the preparation method step b of above-mentioned porous graphene material, the liquid that removes is using the side filtered
Formula.
Preferably, in the preparation method step c of above-mentioned porous graphene material, the heating rate is 1~10 DEG C/min.
Preferably, in the preparation method step c of above-mentioned porous graphene material, the temperature is 600~800 DEG C.
Preferably, in the preparation method step d of above-mentioned porous graphene material, the acid processing is using inorganic acid soak
24~48h.
Further, in the preparation method step d of above-mentioned porous graphene material, the inorganic acid is dilute hydrochloric acid or dilute nitre
Acid.
The present invention also provides the porous graphene materials that the preparation method of above-mentioned porous graphene material is prepared.
The method that the present invention prepares porous graphene material utilizes some metal oxides under high-energy physics inert atmosphere
Redox reaction can occur with graphene basal plane carbon atom, realize and etch pore-creating on graphene basal plane in situ, it is easy to operate
It is easy, and raw material sources are abundant, cheap.The method of the present invention can be by adjusting the compound of metal ion and aoxidizing stone
The weight ratio of ink controls the porosity of product porous graphene material, while can be controlled by adjusting heat treatment temperature
The aperture of porous graphene material, to realize the regulation and control to novel porous grapheme material aperture, porosity, and this is porous
Other performance indicators of grapheme material are suitable with graphene.
Description of the drawings
The XRD diagram of material before the heat treatment of Fig. 1 embodiments 1, after heat treatment, after acid soak.It will be noted from fig. 1 that containing
After heat treatment, sample shows Fe to the graphene oxide composite material of iron ion2O3Characteristic peak, and graphene oxide is reduced
At graphene.After persalt impregnates, typical graphene characteristic peak, Fe have been shown2O3Characteristic peak disappear, illustrate iron content from
The graphene oxide composite material of son can obtain the oxygen discharged when graphene oxide reduction during heat treatment, obtain corresponding metal
Oxide, and the metal oxide can be reacted with hydrochloric acid.
SEM figure (a-b) of Fig. 2 embodiments 1 through the material before and after salt acid soak.It can see from Fig. 2 (a), graphene
Surface inserting that shape is regular, nano particle of well-crystallized, and the edge of each nano particle is by the hole on graphene
Institute's tight, this illustrates that nano particle has vital effect for the formation of hole on graphene.And Fig. 1
XRD has been described that these nano particles are iron oxides.After being impregnated through dilute hydrochloric acid, it can see from Fig. 2 (b), this
A little iron oxides have eliminated, and to expose the hole on graphene completely, obtain novel porous grapheme material.
Fig. 3 embodiments 1-4 and the SEM of comparative example 1-2 products scheme.Wherein, (a) is grapheme material prepared by comparative example 1,
(b) grapheme material prepared for comparative example 2, (c-f) are followed successively by porous graphene material prepared by embodiment 1-4.From Fig. 3
It can be seen that when addition ferric trichloride and heat treatment temperature reach 600 DEG C, the grapheme material of preparation is rich in hole, and hole count
Mesh and pore size can be adjusted by the height of the weight ratio and heat treatment temperature of ferric trichloride and graphite oxide respectively
Control.Illustrate that this method is a kind of method effectively preparing porous graphene material.
Specific implementation mode
A kind of preparation method of novel porous grapheme material, includes the following steps：
1) it under room temperature environment, in deionized water by graphite oxide powder ultrasonic stripping dispersion, is uniformly aoxidized
Graphene aqueous solution；
2) under room temperature environment, in deionized water by the compound dissolving of metal ion, stirring becomes transparent
Uniform solution obtains the compound water solution of metal ion；
3) under room temperature environment, solution prepared by step 2) is slowly added into the solution prepared by step 1), ultrasound
Dispersion obtains mixed liquor；It herein can be according to the change for rationally controlling product graphene porosity, the demand in aperture metal ion
Close the adding proportion relationship of object and graphite oxide；
4) mixed liquor for obtaining step 3) obtains the graphene oxide composite material of metal ion, room by vacuum filtration
Temperature dry a period of time；
5) (such as argon gas) carries out heat to the graphene oxide composite material of the metal ion obtained to step 4) under an inert gas
Processing, heat treatment temperature are 600~1000 DEG C, and the time is 1~4h；After thermal response, the graphite of containing metal oxide is obtained
Alkene material；
6) with diluted acid (such as dilute hydrochloric acid, dust technology) soaking step 5) the obtained grapheme material 24 of containing metal oxide
~48h, then it is washed till neutrality by modes such as dialysis, washing or centrifugations with deionized water, finally in 60~80 DEG C of dryings, obtain
To the porous graphene material of the present invention.
In the preparation method of above-mentioned porous graphene material, a concentration of 1mg/ml after the step 1) graphite oxide solution
~8mg/ml.
In the preparation method of above-mentioned porous graphene material, the compound water solution of the step 2) metal ion it is dense
Degree is 1mg/ml~8mg/ml.
In the preparation method of above-mentioned porous graphene material, the processing of later stage acid needs to use diluted acid (such as dilute hydrochloric acid, dilute nitre
Acid) remove the metal oxide formed.The compound of the metal ion of selection should be water-soluble first in step 2),
Secondary its, which is converted into corresponding oxide and can instead be given birth to common diluted acid, to react, to remove metal oxide to form hole.
Further, the compound of the metal ion is preferably water soluble compound, water with manganese ions containing ferric ion
At least one of the water soluble compound of soluble compound, water-soluble hydrate or copper ions containing zinc ion.More into one
Step, the anion of the compound of the metal ion is preferably chlorion, sulfate ion, nitrate ion or acetate
Any one in ion.
In the preparation method of above-mentioned porous graphene material, step 1) and the step 3) ultrasound are water bath sonicator, are surpassed
The sound time is 30~120min, and ultrasonic power is 150~600W.
In the preparation method of above-mentioned porous graphene material, in step 4), the purpose using vacuum filtration is exactly to remove
Liquid is removed, the filter membrane in suitable aperture should be selected according to actual conditions by filtering film used.It is also possible here to use other modes
Such as oven drying mode.
The present invention is prepared in the method for porous graphene material, graphite oxide powder in deionized water ultrasonic disperse at oxygen
After graphite aqueous solution, because oxygen-containing group present on graphene oxide layer provides a large amount of lone pair electrons, thus will
The adsorption of metal ions being dispersed in water is in graphene oxide basal plane, after vacuum filtration, so that it may to prepare metal ion
Graphene oxide composite material.In subsequent heat treatment process, with the raising of temperature, graphene oxide is heated to lose oxygen-containing official
The metal ion that energy group is restored, and is adsorbed on graphene oxide basal plane can obtain oxygen and become metal oxide.With temperature
Degree is increased to 600~1000 DEG C, and with the carbon atom on graphene basal plane redox reaction, carbon atom quilt occur for metal oxide
It is oxidized to gaseous hydrocarbon, to realize the original position etching to graphene basal plane, i.e. heat treatment reaction pore-creating.Most
Afterwards use acid elution material, so that it may to remove metal oxide, the hole on graphene is exposed completely, i.e., acid elution at
Hole.
Further, in this process, if the metal ion content on material is less, after thermally treated, graphene
On hole number will be less；When reverse metal ion concentration is higher, after thermally treated, the hole number on graphene is just
It can increase.Therefore by regulating and controlling the compound of metal ion and the weight ratio of graphite oxide novel porous stone can be controlled
The number of perforations of black alkene material.In actual production preparation process, it can be required according to the difference to porosity, reasonably adjust and contain
The additive amount of metal ion compound and graphene oxide.
Meanwhile the heat treatment temperature in above-mentioned preparation process described in step 5) is 600~1000 DEG C, the time is 1~4h.Heat
The metal ion being adsorbed in processing procedure on graphite oxide basal plane can obtain oxygen and become metal oxide, and metal oxide meeting
With the raising of temperature, there is the process that particle constantly reunites, grows up.Metal oxide is sent out with the carbon atom on graphene basal plane
Raw redox reaction etches pore-creating.In the process, the grain size of metal oxide is bigger, and the hole etched is bigger, conversely,
The hole etched is smaller.Therefore the tune to novel porous grapheme material aperture can be realized by regulating and controlling heat treatment temperature
Control.
Further, with the raising of temperature, metal oxide particle is reunited, and products obtained therefrom aperture becomes larger, at this time when adding
The timing of raw material one entered, the number of perforations of products obtained therefrom will reduce, if need at this time more number of perforations may just needs it is more
The compound of metal ion is added；Vice versa.So the balance between number of perforations and aperture is needed by depending on demand
The aperture of what range selects suitable temperature, wants to obtain certain number of perforations again such as under this aperture, then by controlling raw material
Proportioning determine.
In the method for the present invention, when temperature is 600 DEG C, gained aperture is in 20nm or so, when temperature is 800 DEG C, gained
Graphene aperture is 150~300nm or so, and different temperature can be adjusted according to the demand to product aperture.
The present invention is specifically described in the following with reference to the drawings and specific embodiments.Following embodiment is served only for the present invention
It is further described, does not do any restriction to invention content itself, the person skilled in the art in the field can be according to the present invention
Make some nonessential modifications and adaptations.
Embodiment 1
Under room temperature environment, by 6mg graphite oxides 300W water bath sonicators 60min in deionized water, it is equal to obtain 1mg/ml
Even graphene oxide solution.Ferric trichloride is dissolved in deionized water, the transparent uniform solution of 2mg/ml is configured to.Then
It is slowly added into above-mentioned graphene oxide solution, uniform mixed liquor, wherein ferric trichloride is obtained through 300W water bath sonicators 30min
Weight ratio with graphene oxide is 1 ﹕ 1.Then through being filtered by vacuum into the graphene oxide composite material containing iron ion.Drying at room temperature
After 12h, the heat treatment under argon gas atmosphere is carried out to material, heat treatment temperature is 800 DEG C, time 2h.After thermal response is complete, use
Dilute hydrochloric acid impregnates 48h, and novel porous grapheme material is obtained by it in 80 DEG C of dryings with deionized water dialysis to neutrality.
Embodiment 2
Under room temperature environment, by 6mg graphite oxides 300W water bath sonicators 60min in deionized water, it is equal to obtain 1mg/ml
Even graphene oxide solution.Ferric trichloride is dissolved in deionized water, the transparent uniform solution of 2mg/ml is configured to.Then
It is slowly added into above-mentioned graphene oxide solution, uniform mixed liquor, wherein ferric trichloride is obtained through 300W water bath sonicators 30min
Weight ratio with graphene oxide is 2 ﹕ 3.Then through being filtered by vacuum into the graphene oxide composite material containing iron ion.Drying at room temperature
After 12h, the heat treatment under argon gas atmosphere is carried out to material, heat treatment temperature is 800 DEG C, time 2h.After thermal response is complete, use
Dilute hydrochloric acid impregnates 48h, and deionized water dialysis is used in combination to obtain novel porous grapheme material by it in 80 DEG C of dryings to neutrality.
Embodiment 3
Under room temperature environment, by 6mg graphite oxides 300W water bath sonicators 60min in deionized water, it is equal to obtain 1mg/ml
Even graphene oxide solution.Ferric trichloride is dissolved in deionized water, the transparent uniform solution of 2mg/ml is configured to.Then
It is slowly added into above-mentioned graphene oxide solution, uniform mixed liquor, wherein ferric trichloride is obtained through 300W water bath sonicators 30min
Weight ratio with graphene oxide is 1 ﹕ 3.Then through being filtered by vacuum into the graphene oxide composite material containing iron ion.Drying at room temperature
After 12h, the heat treatment under argon gas atmosphere is carried out to material, heat treatment temperature is 800 DEG C, time 2h.After thermal response is complete, use
Dilute hydrochloric acid impregnates 48h, and deionized water dialysis is used in combination to obtain novel porous grapheme material by it in 80 DEG C of dryings to neutrality.
Embodiment 4
Under room temperature environment, by 6mg graphite oxides 300W water bath sonicators 60min in deionized water, it is equal to obtain 1mg/ml
Even graphene oxide solution.Ferric trichloride is dissolved in deionized water, the transparent uniform solution of 2mg/ml is configured to.Then
It is slowly added into above-mentioned graphene oxide solution, uniform mixed liquor, wherein ferric trichloride is obtained through 300W water bath sonicators 30min
Weight ratio with graphene oxide is 1 ﹕ 1.Then through being filtered by vacuum into the graphene oxide composite material containing iron ion, drying at room temperature
After 12h, the heat treatment under argon gas atmosphere is carried out to material, heat treatment temperature is 600 DEG C, time 2h.After thermal response is complete, use
Dilute hydrochloric acid impregnates 48h, and deionized water dialysis is used in combination to obtain novel porous grapheme material by it in 80 DEG C of dryings to neutrality.It is right
Ratio 1
Under room temperature environment, by 6mg graphite oxides 300W water bath sonicators 60min in deionized water, it is equal to obtain 1mg/ml
Even graphene oxide solution.Then through vacuum filtration at graphene oxide composite material, after drying at room temperature 12h, argon is carried out to material
Heat treatment under gas atmosphere, heat treatment temperature are 800 DEG C, time 2h.After thermal response is complete, 48h is impregnated with dilute hydrochloric acid, is used in combination
Deionized water dialysis obtains grapheme material to neutrality by it in 80 DEG C of dryings.
Comparative example 2
Under room temperature environment, by 6mg graphite oxides 300W water bath sonicators 60min in deionized water, it is equal to obtain 1mg/ml
Even graphene oxide solution.Ferric trichloride is dissolved in deionized water, the transparent uniform solution of 2mg/ml is configured to.Then
It is slowly added into above-mentioned graphene oxide solution, uniform mixed liquor, wherein ferric trichloride is obtained through 300W water bath sonicators 30min
Weight ratio with graphene oxide is 1 ﹕ 1.Then through being filtered by vacuum into the graphene oxide composite material containing iron ion, drying at room temperature
After 12h, the heat treatment under argon gas atmosphere is carried out to material, heat treatment temperature is 400 DEG C, time 2h.After thermal response is complete, use
Dilute hydrochloric acid impregnates 48h, and deionized water dialysis is used in combination to obtain grapheme material by it in 80 DEG C of dryings to neutrality.
Have aperture and porosity adjustable using porous graphene material prepared by preparation method of the present invention
Feature.And this has important advantage in the application of novel energy-storing Material Field for it.Another considerable advantage of the method for the present invention
It is that can prepare porous graphene based composites, these are advantageous using the novel porous grapheme material as basis material
In the promotion and application of this novel porous grapheme material preparation method.
Claims (10)
1. the preparation method of porous graphene material, it is characterised in that：Include the following steps：
A, graphite oxide powder is dispersed in water by ultrasound stripping, obtains graphene oxide water solution；By metal ion
Compound be dissolved in water, obtain the compound water solution of metal ion；
B, by two kinds of solution mixings of step a, liquid is removed, solid is obtained；
C, under an inert gas, solid is warming up to 600~1000 DEG C of 1~4h of heat preservation；
D, acid handles, is washed till neutrality, is drying to obtain porous graphene material.
2. the preparation method of porous graphene material according to claim 1, it is characterised in that：In step a, the ultrasound
Time is 30~120min, and ultrasonic power is 150~600W.
3. the preparation method of porous graphene material according to claim 1, it is characterised in that：In step a, the oxidation
A concentration of 1~8mg/mL of graphene aqueous solution；A concentration of 1~8mg/mL of the compound water solution of the metal ion.
4. the preparation method of porous graphene material according to claim 1, it is characterised in that：It is described containing gold in step a
The compound for belonging to ion is water-soluble, and when the metal ion is converted into corresponding oxide, which can be anti-with diluted acid
It answers.
5. the preparation method of porous graphene material according to claim 4, it is characterised in that：It is described containing gold in step a
The compound for belonging to ion is water soluble compound containing ferric ion, water soluble compound with manganese ions, containing zinc ion
At least one of the water soluble compound of water soluble compound or copper ions.
6. the preparation method of porous graphene material according to claim 4 or 5, it is characterised in that：It is described in step a
The anion of the compound of metal ion is arbitrary in chlorion, sulfate ion, nitrate ion or acetate ion
It is a kind of.
7. the preparation method of porous graphene material according to claim 1, it is characterised in that：In step b, the mixing
By the way of ultrasound, ultrasonic time is 30~120min, and ultrasonic power is 150W~600W.
8. the preparation method of porous graphene material according to claim 1, it is characterised in that：In step c, the heating
Rate is 1~10 DEG C/min.
9. the preparation method of porous graphene material according to claim 1, it is characterised in that：In step d, at the acid
Reason is using inorganic 24~48h of acid soak.
10. the porous graphene being prepared by the preparation method of claim 1~9 any one of them porous graphene material
Material.
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| CN109368620A (en) * | 2018-12-11 | 2019-02-22 | 中国科学院兰州化学物理研究所 | A kind of preparation method of extra small sub-nanometer hole porous graphene |
| CN109802117A (en) * | 2019-01-24 | 2019-05-24 | 青岛大学 | A kind of γ-Fe2O3The porous graphene composite material and preparation method thereof of etching and application |
| CN111732102A (en) * | 2019-12-04 | 2020-10-02 | 中国科学院上海硅酸盐研究所 | Method for preparing porous carbon material by ruthenium particle assisted etching in strong alkaline environment |
| CN111807353A (en) * | 2020-07-17 | 2020-10-23 | 北京石墨烯研究院 | Porous graphene and preparation method and application thereof |
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