CN104591176B - A kind of preparation method of Graphene - Google Patents
A kind of preparation method of Graphene Download PDFInfo
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- CN104591176B CN104591176B CN201510057842.5A CN201510057842A CN104591176B CN 104591176 B CN104591176 B CN 104591176B CN 201510057842 A CN201510057842 A CN 201510057842A CN 104591176 B CN104591176 B CN 104591176B
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Abstract
The invention provides a kind of preparation method of Graphene, comprises the following steps：A) biological material, anion surfactant and water are mixed, hydro-thermal reaction is carried out, presoma is obtained, the temperature of the hydro-thermal reaction is 150～250 DEG C, and the time of the hydro-thermal reaction is 1～24 hour；B) by metallic catalyst and step A) presoma that obtains mixes, and obtains the presoma containing metallic catalyst；C) by step B) presoma containing metallic catalyst that obtains heated, and obtains Graphene.The preparation method that the present invention is provided is with biological material as carbon source, biological material reaction under hydrothermal conditions can produce gaseous products, anion surfactant can be enriched with the biological material in these bubbles and body phase solution, carbon hollow ball is formed by template of bubble, obtain the presoma with relatively thin spherical shell layer and high surfaces activity, easily it is catalyzed by metallic catalyst, obtains the higher Graphene of degree of graphitization.
Description
Technical field
The invention belongs to material with carbon element technical field, more particularly to a kind of preparation method of Graphene.
Background technology
Graphene is two-dimensional material most thin in the world, and thickness is only 20 a ten thousandths of hairline, and its intensity is but
Know highest in material, 100 times more taller than best iron and steel, it is steel that the power needed for the single-layer graphene of same cross-sectional is broken
200 times of material.Research finds that the maximum pressure that the Graphene of 100nm can bear has reached about 2.9 micro- oxen, equivalent to applying
The pressure of 55 newton can just make the Graphene of 1m length rupture.If making the thick graphene films of 100nm, about 20,000 Ns can be born
The pressure for pausing, then about two tons of heavy articles can be carried with packaging bag made by Graphene, it is the world fully to indicate Graphene
The material of upper maximum intensity.
In recent years, people constantly explore new method to improve the yield of Graphene, at present, can be prepared using various methods
Obtain grapheme material powder, such as mechanical stripping method, oxidation-reduction method, crystal epitaxy method, chemical vapour deposition technique, have
Machine synthetic method and stripping CNT method etc..In these methods, mechanical stripping method and epitaxial growth method preparation efficiency are very low, difficult
To meet large-scale needs.Although chemical vapour deposition technique can obtain the continuous graphene film of large scale, only it is suitable for
In micro-nano electronic device or transparent conductive film, the extensive need in energy storage material and functional composite material field can not be but met
Ask.It is more stable in oxidation-reduction method, using relatively broad, but due to needing in oxidation-reduction process using substantial amounts of strong
Acid and strong oxidizer, such as red fuming nitric acid (RFNA), the concentrated sulfuric acid, potassium permanganate or potassium chlorate etc., not only bring very big pollution, also can to environment
Certain danger is brought to operating process.
Catalytic activation method is a kind of new method for preparing Graphene, catalytic activation method be with biological material as carbon source,
The functional group's physical absorption enriched using biological surface or ion exchange metal ion, are mixed with pore creating material, in high temperature inert
It is carbonized under atmosphere, prepares porous graphene.As catalytic activation method does not use strong acid and strong oxidizer, therefore, environmental pollution
It is less, but the Graphene prepared using existing catalytic activation technology can only make material surface graphitization, biological material
The overall degree of graphitization of material is not high, affects product quality.
The content of the invention
It is an object of the invention to provide a kind of preparation method of Graphene, is obtained using the preparation method of present invention offer
Graphene degree of graphitization it is higher, the product quality for obtaining is preferable.
The invention provides a kind of preparation method of Graphene, comprises the following steps：
A) biological material, anion surfactant and water are mixed, hydro-thermal reaction is carried out, is obtained presoma, it is described
The temperature of hydro-thermal reaction is 150～250 DEG C, and the time of the hydro-thermal reaction is 1～24 hour；
B) by metallic catalyst and step A) presoma that obtains mixes, and obtains the forerunner containing metallic catalyst
Body；
C) by step B) presoma containing metallic catalyst that obtains heated, and obtains Graphene.
Preferably, during the biological material includes glucose, sucrose, fructose, sorbose, galactolipin and mannose
One or more.
Preferably, the anion surfactant includes lauryl sodium sulfate, dodecyl sodium sulfate, dodecyl
One or more in benzene sulfonic acid sodium salt and odium stearate.
Preferably, the biological material and the mass ratio of the anion surfactant are (10～50)：1.
Preferably, step B) in metallic catalyst include the one kind or several in molysite, ferrous salt, nickel salt and cobalt salt
Kind.
Preferably, the metallic catalyst and step A) mass ratio of presoma that obtains is (0.01～1)：1.
Preferably, step C) in heating temperature be 800～1200 DEG C；
The time of the heating is 1～5 hour.
Preferably, step A) presoma that obtains is hollow ball structure, the thickness of the hollow ball spherical shell is 2～
30nm。
Preferably, step A) specifically include：
Biological material, anion surfactant, hydrofluoric acid and water are mixed, hydro-thermal reaction are carried out, is obtained presoma,
The temperature of the hydro-thermal reaction is 150～250 DEG C, and the time of the hydro-thermal reaction is 1～24 hour；
The molar concentration of the hydrofluoric acid is 0.01～2mol/L.
Preferably, step B) specifically include：By pore creating material and step A) obtain containing metallic catalyst
Presoma mixes, and is heated, obtains Graphene；
During the pore creating material includes water vapour, potassium hydroxide, potassium oxide, zinc chloride, phosphoric acid, sodium oxide molybdena and NaOH
One or more；
The pore creating material and step A) in biological material mass ratio be (1～5)：1.
The invention provides a kind of preparation method of Graphene, comprises the following steps：A) by biological material, anion table
Face activating agent and water mixing, carry out hydro-thermal reaction, obtain presoma, and the temperature of the hydro-thermal reaction is 150～250 DEG C, described
The time of hydro-thermal reaction is 1～24 hour；B) by metallic catalyst and step A) presoma that obtains mixes, contained
The presoma of metallic catalyst；C) by step B) presoma containing metallic catalyst that obtains heated, and obtains stone
Black alkene.The preparation method that the present invention is provided with biological material as carbon source, can produce by biological material reaction under hydrothermal conditions
Raw gaseous products, such as CO2, CO and H2The life in these bubbles and body phase solution can be enriched with Deng, the anion surfactant
Material, and carbon hollow ball is formed by template of bubble, the carbon hollow ball shell for obtaining is relatively thin and is rich in a large amount of anion
Surfactant, anion surfactant are dissociated into electronegative group in aqueous, it is easier to adsorb iron, nickel etc. and carry
The metal ion of positive charge, in follow-up heating process, carbon hollow ball is easier to be catalyzed by metallic catalyst, obtains graphitization
The higher Graphene of degree.
Further, the present invention can be to carry out fluorination treatment in water-heat process, and the carbon hollow ball to obtaining carries out fluorine
Change modified so that carbon hollow ball has higher electronegativity, be more beneficial for adsorbing the metallic of positively charged.
Description of the drawings
In order to be illustrated more clearly that the embodiment of the present invention or technical scheme of the prior art, below will be to embodiment or existing
Accompanying drawing to be used needed for having technology description is briefly described, it should be apparent that, drawings in the following description are only this
Inventive embodiment, for those of ordinary skill in the art, on the premise of not paying creative work, can be with basis
The accompanying drawing of offer obtains other accompanying drawings.
Fig. 1 is the TEM figures of the presoma that the embodiment of the present invention 1 is obtained；
Fig. 2 is the SEM figures of the Graphene that the embodiment of the present invention 1 is obtained；
Fig. 3 is the TEM figures of the Graphene that the embodiment of the present invention 1 is obtained；
Fig. 4 is the specific surface area figure of the Graphene that the embodiment of the present invention 1 is obtained；
Fig. 5 is the porosity figure of the Graphene that the embodiment of the present invention 1 is obtained；
Fig. 6 is the Raman spectrum of the Graphene that the embodiment of the present invention 1 is obtained；
Fig. 7 is the SEM figures of the presoma that the embodiment of the present invention 2 is obtained；
Fig. 8 is the TEM figures of the presoma that comparative example of the present invention 1 is obtained；
Fig. 9 is the SEM figures of the Graphene that comparative example of the present invention 1 is obtained；
Figure 10 is the TEM figures of the Graphene that comparative example of the present invention 1 is obtained.
Specific embodiment
The invention provides a kind of preparation method of Graphene, comprises the following steps：
A) biological material, anion surfactant and water are mixed, hydro-thermal reaction is carried out, is obtained presoma, it is described
The temperature of hydro-thermal reaction is 150～250 DEG C, and the time of the hydro-thermal reaction is 1～24 hour；
B) by metallic catalyst and step A) presoma that obtains mixes, and obtains the forerunner containing metallic catalyst
Body；
C) by step B) presoma containing metallic catalyst that obtains heated, and obtains Graphene.
The degree of graphitization of Graphene that the preparation method provided using the present invention is obtained is higher, the product quality for obtaining compared with
It is good.
Biological material, anion surfactant and water are mixed by the present invention, are carried out hydro-thermal reaction, are obtained presoma,
The biological material, anion surfactant and water are preferably mixed by the present invention, carry out ultrasound, then by mixing that ultrasound is crossed
Compound carries out hydro-thermal reaction, obtains presoma.In the present invention, the biological material preferably includes glucose, sucrose, fruit
One or more in sugar, sorbose, galactolipin and mannose, more preferably including the one kind in glucose, sucrose and mannose
Or it is several；The anion surfactant preferably includes lauryl sodium sulfate, dodecyl sodium sulfate, detergent alkylate sulphur
One or more in sour sodium and odium stearate, more preferably including lauryl sodium sulfate and/or neopelex；With
The biological material and anion surfactant mixing water used is preferably deionized water.In the present invention, the life
Material is (10～50) with the mass ratio of the anion surfactant：1, more preferably (12～30)：1, most preferably
For 15:1；The biological material is preferably 1 with the mass ratio of water：(8～15), more preferably 1：(9～13), most preferably 1：
(10～12).
In order that to presoma there is higher electronegativity, the present invention is preferably by the biological material, anion
Surfactant is mixed with hydrofluoric acid solution, is carried out ultrasound, is obtained presoma.In the present invention, the hydrofluoric acid solution rubs
Your concentration is preferably 0.01～2mol/L, most preferably more preferably 0.05～1.5mol/L, 0.1～0.5mol/L, the present invention
There is no special restriction to the consumption of the hydrofluoric acid.
In the present invention, the temperature of the ultrasound is preferably 20～30 DEG C, more preferably 25 DEG C；The time of the ultrasound is excellent
Elect 3～10min, more preferably 5～8min as.
After completing the ultrasound, the mixture that ultrasound is obtained by the present invention carries out hydro-thermal reaction, obtains presoma.At this
In bright, the hydro-thermal reaction is referred in the pressure vessel of sealing, with water as solvent, the change carried out under conditions of HTHP
Learn reaction.In the present invention, the temperature of the hydro-thermal reaction be 150～250 DEG C, preferably 170～210 DEG C, more preferably 180
℃；Preferably 1～24 hour time of the hydro-thermal reaction, more preferably 8～20 hours, most preferably 10～18 hours, most
Most preferably 12～16 hours；The present invention does not have special restriction to the pressure of the hydro-thermal reaction, makes the closed pressure
Temperature in container reaches above-mentioned requirements.The present invention preferably carries out the hydro-thermal reaction in a kettle..In the present invention,
The thickness that the presoma that the hydro-thermal reaction is obtained has hollow ball structure, the hollow ball spherical shell is preferably 2～30nm, more excellent
Elect 5～20nm, most preferably 10～15nm as.
After completing the hydro-thermal reaction, the presoma for obtaining preferably is dried by the present invention, obtains dry presoma.
In the present invention, the temperature of the drying is preferably 60～100 DEG C, more preferably 70～90 DEG C, most preferably 80 DEG C；It is described dry
The dry time is preferably 8～12 hours, more preferably 10～11 hours.
After obtaining presoma, metallic catalyst is mixed by the present invention with the presoma for obtaining, and is obtained containing metallic catalyst
Presoma.In the present invention, the metallic catalyst preferably includes the one kind or several in molysite, ferrous salt, nickel salt and cobalt salt
Kind, more preferably in iron chloride, nickel chloride, nickel acetate, ferric acetate, ferric sulfate, nickel sulfate, the potassium ferricyanide and potassium ferrocyanide
One or more, most preferably including one or more in nickel chloride, iron chloride, the potassium ferricyanide and nickel acetate；The metal is urged
Agent is preferably (0.01～1) with the mass ratio of the presoma：1.Present invention preferably employs metal catalyst solution with it is described
Presoma mixes, and obtains the presoma containing metallic catalyst.In the present invention, the molar concentration of the metal catalyst solution
Preferably 0.01～0.1mol/L, more preferably 0.05～0.08mol/L.
The presoma is preferably impregnated in the metal catalyst solution by the present invention, combines the metallic catalyst
To on the presoma, in the present invention, the metallic catalyst is mainly combined with the presoma by way of deposition, together
When also have part metals catalyst to be combined with the presoma by the suction-operated between functional group.In the present invention, institute
The time for stating dipping is preferably 1～10 hour, more preferably 2～8 hours.After completing above-mentioned dipping, the present invention preferably will dipping
Solution afterwards is filtered, and is removed liquid, is obtained solid.In the present invention, it is described be filtered into it is well known to those skilled in the art
Method.
After completing to filter, the solid being filtrated to get preferably is dried by the present invention, and obtain drying contains metal
The presoma of catalyst.In the present invention, 60～100 DEG C are preferably to the temperature of the drying of the solid being filtrated to get, more
Preferably 70～90 DEG C, most preferably 80 DEG C；The time of the drying of the solid being filtrated to get is preferably 8～12 hours,
More preferably 10～11 hours.
After obtaining the presoma containing metallic catalyst, the presoma containing metallic catalyst is carried out adding by the present invention
Heat, obtains Graphene.The presoma containing metallic catalyst is preferably mixed by the present invention with pore creating material, is heated, is obtained
To Graphene.In the present invention, the pore creating material preferably includes water vapour, potassium hydroxide, potassium oxide, zinc chloride, phosphoric acid, oxidation
One or more in sodium and NaOH, more preferably including one or more in NaOH, potassium hydroxide and vapor,
Most preferably potassium hydroxide；The pore creating material is preferably (1～5) with the mass ratio of the presoma containing metallic catalyst：
1, more preferably 2:1.
After the present invention is by the pore creating material and the mixing of the presoma containing metallic catalyst, preferably first it is dried, then
Heated again, obtained Graphene.In the present invention, the pore creating material and the precursor mixture containing metallic catalyst is dry
It is dry for method well known to those skilled in the art.
Mixing of the present invention preferably under protective gas atmosphere to the pore creating material and the presoma containing metallic catalyst
Thing is heated, and obtains Graphene.In the present invention, the protective gas is preferably inert gas and/or nitrogen.In the present invention
In, the temperature of the heating is preferably 800～1200 DEG C, more preferably 900～1100 DEG C, most preferably 1000 DEG C；It is described to add
The time of heat is preferably 1～5 hour, more preferably 2～4 hours.Present invention preferably employs the method for heating up reaches above-mentioned heating
Temperature, the speed of the intensification are preferably 3～8 DEG C/min, most preferably more preferably 4～6 DEG C/min, 5 DEG C/min.
After completing the heating, the product that heating is obtained preferably is carried out pickling and filtration by the present invention successively, to remove which
The metallic catalyst of middle residual.In the present invention, the acid solution used by the pickling is preferably the one kind in hydrochloric acid, sulfuric acid and nitric acid
Or two kinds, the dip time of the pickling is preferably 0.5～8 hour, more preferably 1～7 hour, most preferably 2～6 hours.
After completing the pickling, the product after pickling is preferably carried out separation of solid and liquid by the present invention, is removed liquid, is obtained graphite
Alkene.In the present invention, the separation of solid and liquid is preferably filtered, described to be filtered into the technological means that those skilled in the art commonly use.
After completing the separation of solid and liquid, the product that the separation of solid and liquid is obtained preferably is dried by the present invention, obtains stone
Black alkene.In the present invention, the drying is preferably dried, and the temperature of the drying is preferably 100～150 DEG C, and more preferably 90
～140 DEG C, most preferably 100～120 DEG C；The time of the drying is preferably 8～12 hours, more preferably 10 hours.
The specific surface area of the Graphene obtained according to above-mentioned preparation method is preferably 1000～2000cm3/ g, more preferably
1200～1800cm3/g；The aperture of the Graphene is preferably 1～10nm, most preferably more preferably 2～9nm, 3～8nm.
After obtaining Graphene, Graphene has been carried out ESEM detection (SEM) by the present invention, is as a result shown, the present invention is carried
For Graphene be lamella pattern, degree of graphitization is higher, and graphenic surface is distributed with substantial amounts of micropore.
The present invention adopts full-automatic specific surface area and micropore Physisorption Analyzer to have detected the Graphene that the present invention is obtained
Specific surface area and porosity, as a result show, the porous graphene specific surface for obtaining is larger, in 1000～2000cm3/g；Hole
Distribution is mainly 1～10nm.
The present invention has carried out Raman spectrum detection to the Graphene for obtaining, and as a result shows, the porous graphene for obtaining has
Certain degree of graphitization.
The invention provides a kind of preparation method of Graphene, comprises the following steps：A) by biological material, anion table
Face activating agent and water mixing, carry out hydro-thermal reaction, obtain presoma, and the temperature of the hydro-thermal reaction is 150～250 DEG C, described
The time of hydro-thermal reaction is 1～24 hour；B) by metallic catalyst and step A) presoma that obtains mixes, contained
The presoma of metallic catalyst；C) by step B) presoma containing metallic catalyst that obtains heated, and obtains stone
Black alkene.The preparation method that the present invention is provided with biological material as carbon source, can produce by biological material reaction under hydrothermal conditions
Raw gaseous products, such as CO2, CO and H2The life in these bubbles and body phase solution can be enriched with Deng, the anion surfactant
Material, and carbon hollow ball is formed by template of bubble, the carbon hollow ball shell for obtaining is relatively thin and is rich in a large amount of anion
Surfactant, anion surfactant are dissociated into electronegative group in aqueous, it is easier to adsorb iron, nickel etc. and carry
The metal ion of positive charge, in follow-up heating process, carbon hollow ball is easier to be catalyzed by metallic catalyst, obtains graphitization
The higher Graphene of degree.
Further, the present invention can be to carry out fluorination treatment in water-heat process, and the carbon hollow ball to obtaining carries out fluorine
Change modified so that carbon hollow ball has higher electronegativity, be more beneficial for adsorbing the metallic of positively charged.
In order to further illustrate the present invention, a kind of preparation method of Graphene that with reference to embodiments present invention is provided
It is described in detail, but limiting the scope of the present invention can not be understood as.
Embodiment 1
10g glucose, 1g lauryl sodium sulfate are taken, and 150ml concentration are added for the hydrofluoric acid aqueous solution of 0.01mol/l
In, it is then that the glucose solution for obtaining is ultrasonic 5 minutes, pour in reactor, hydro-thermal reaction is carried out at 180 DEG C, react 10h
Afterwards, 80 DEG C of dryings, obtain presoma.
1g presomas are taken, 100ml is added to and is contained in 1g potassium ferricyanide solutions, ultrasound 15 minutes stands 4h, filters, will
The solid being filtrated to get is dried at 80 DEG C, obtains presoma containing iron ion.According to the presoma containing iron ion and the quality of KOH
Than 1:1 ratio is mixed with KOH, is dried, and 2h is calcined under 1000 DEG C, inert atmosphere, and heating rate is 5 DEG C/min, is calcined
The salt acid elution of the product Jing 1mol/L for arriving, filters, and the solid being filtrated to get is dried at 120 DEG C, porous graphene is obtained.
The presoma that the present invention is obtained to the present embodiment has carried out transmission electron microscope detection (TEM), as a result as shown in figure 1, Fig. 1
The TEM figures of the presoma obtained for the embodiment of the present invention 1；As seen from Figure 1, the presoma that the present embodiment is obtained is hollow ball
Structure, thickness are 2～30nm.
The Graphene that the present invention is obtained to the present embodiment has carried out ESEM detection (SEM), as a result as shown in Fig. 2 Fig. 2
The SEM figures of the porous graphene obtained for the embodiment of the present invention 1；
The Graphene that the present invention is obtained to the present embodiment has carried out transmission electron microscope detection (TEM), as a result as shown in figure 3, Fig. 3
The TEM figures of the Graphene obtained for the embodiment of the present invention 1.The graphite that the embodiment of the present invention 1 is obtained can be seen that by Fig. 2 and Fig. 3
Alkene material is three-dimensional lamella pattern, and porous graphene surface distributed has substantial amounts of micropore, and size is mainly 1～10nm.
The present invention tests the specific surface area of the Graphene that the present embodiment is obtained according to above-mentioned technical proposal, as a result such as Fig. 4
Shown, Fig. 4 is the specific surface area figure of the Graphene that the embodiment of the present invention 1 is obtained.As seen from Figure 4, the Graphene ratio for obtaining
Surface is larger, between 1000～2000cm3/g.
The present invention tests the porosity of the Graphene that the present embodiment is obtained according to above-mentioned technical proposal, as a result such as Fig. 5 institutes
Show, Fig. 5 is the porosity figure of the Graphene that the embodiment of the present invention 1 is obtained.As seen from Figure 5, distribution of pores predominantly 1～
10nm。
The Graphene that obtains to the present embodiment of the present invention has carried out Raman spectrum (Raman) detection, as a result as shown in fig. 6,
Fig. 6 is the Raman spectrum of the Graphene that the embodiment of the present invention 1 is obtained.As seen from Figure 6, the Graphene for obtaining has certain
Degree of graphitization.
Embodiment 2
20g glucose, 1g neopelexes are taken, 150ml deionized waters are added, then will be the glucose for obtaining molten
Liquid ultrasound 5 minutes, pours in reactor, and hydro-thermal reaction is carried out at 150 DEG C, and after reaction 6h, 80 DEG C of dryings obtain presoma.
1g presomas are taken, is added in 100ml ferric chloride solutions containing 0.5g, ultrasound 15 minutes stands 10h, filters, incited somebody to action
The solid that filter is obtained is dried at 80 DEG C, obtains presoma containing iron ion.2h, heating rate are calcined under 800 DEG C, inert atmosphere
For 5 DEG C/min, the salt acid elution of the product Jing 1mol/L for obtaining is calcined, filtered, the solid being filtrated to get is done at 120 DEG C
It is dry, obtain Graphene.
The presoma that the present invention is obtained to the present embodiment has carried out ESEM detection (SEM), as a result as shown in fig. 7, Fig. 7
The SEM figures of the presoma obtained for the embodiment of the present invention 2；As seen from Figure 7, the presoma that the present embodiment is obtained is tied for lamella
Structure.
Embodiment 3
50g sucrose, 1g lauryl sodium sulfate are taken, 300ml deionized waters are added, then by the sucrose solution for obtaining ultrasound
5 minutes, pour in reactor, hydro-thermal reaction is carried out at 250 DEG C, after reaction 24h, 80 DEG C of dryings obtain presoma.
1g presomas are taken, is added in nickel chloride solutions of the 100ml containing 0.8g, ultrasound 15 minutes stands 4h, filters, will
The solid being filtrated to get is dried at 80 DEG C, obtains presoma containing nickel ion.According to the presoma containing nickel ion and the quality of KOH
Than 1:3 ratio is mixed with KOH, is dried, and 2h is calcined under 1200 DEG C, inert atmosphere, and heating rate is 5 DEG C/min, is calcined
The salt acid elution of the product Jing 1mol/L for arriving, filters, and the solid being filtrated to get is dried at 120 DEG C, porous graphene is obtained.
Embodiment 4
30g glucose, 1g dodecyl sodium sulfates are taken, and 300ml concentration are added for the hydrofluoric acid aqueous solution of 0.01mol/l
In, it is then that the glucose solution for obtaining is ultrasonic 5 minutes, pour in reactor, hydro-thermal reaction is carried out at 250 DEG C, react 1h
Afterwards, 80 DEG C of dryings, obtain presoma.
1g presomas are taken, are added in potassium ferricyanide solutions of the 100ml containing 0.4g, ultrasound 15 minutes stands 4h, filters,
The solid being filtrated to get is dried at 80 DEG C, presoma containing iron ion is obtained.According to the presoma containing iron ion and the matter of KOH
Amount compares 1:2 ratio is mixed with KOH, is dried, and 2h is calcined under 1000 DEG C, inert atmosphere, and heating rate is 5 DEG C/min, is calcined
The salt acid elution of the product Jing 1mol/L for obtaining, filters, and the solid being filtrated to get is dried at 120 DEG C, Graphene is obtained.
Embodiment 5
40g mannoses, 1g neopelexes are taken, in adding 300ml concentration for the hydrofluoric acid aqueous solution of 2mol/l,
Then it is the mannose solution for obtaining is ultrasonic 5 minutes, pour in reactor, hydro-thermal reaction is carried out at 200 DEG C, after reaction 5h,
60 DEG C of dryings, obtain presoma.
1g presomas are taken, is added in potassium ferricyanide solutions of the 100ml containing 1g, ultrasound 15 minutes stands 4h, filters, will
The solid being filtrated to get is dried at 80 DEG C, obtains presoma containing iron ion.According to the presoma containing iron ion and the quality of KOH
Than 1:5 ratio is mixed with KOH, is dried, and 2h is calcined under 1000 DEG C, inert atmosphere, and heating rate is 5 DEG C/min, is calcined
The salt acid elution of the product Jing 1mol/L for arriving, filters, and the solid being filtrated to get is dried at 120 DEG C, porous graphene is obtained.
Embodiment 6
10g glucose, 1g lauryl sodium sulfate are taken, in 300ml concentration being added for the hydrofluoric acid aqueous solution of 1mol/l, so
It is afterwards that the glucose solution for obtaining is ultrasonic 5 minutes, pour in reactor, hydro-thermal reaction is carried out at 170 DEG C, after reaction 16h, 80
DEG C drying, obtains presoma.
1g presomas are taken, are added in potassium ferricyanide solutions of the 100ml containing 0.01g, ultrasound 15 minutes stands 4h, filters,
The solid being filtrated to get is dried at 80 DEG C, presoma containing iron ion is obtained.According to the presoma containing iron ion and the matter of KOH
Amount compares 1:1 ratio is mixed with KOH, is dried, and 1h is calcined under 900 DEG C, inert atmosphere, and heating rate is 5 DEG C/min, is calcined
The salt acid elution of the product Jing 1mol/L for arriving, filters, and the solid being filtrated to get is dried at 120 DEG C, porous graphene is obtained.
Comparative example 1
10g glucose is taken, addition 150ml deionized waters pour the glucose solution for obtaining ultrasound into reactor after 5 minutes
In, hydro-thermal reaction is carried out at 180 DEG C, after reaction 12h, reactant liquor is dried at 80 DEG C, presoma is obtained.
1g presomas are taken, is added in potassium ferricyanide solutions of the 100mL containing 1g, ultrasound 15 minutes stands 4h, filters, will
The solid being filtrated to get is dried at 80 DEG C, obtains presoma containing iron ion.In mass ratio 1:1 is mixed with KOH, be dried after
1000 DEG C, calcine 2h under nitrogen atmosphere, heating rate is 5 DEG C/min, calcines the salt acid elution of the product Jing 1mol/L for obtaining, mistake
Filter, 120 DEG C of dryings obtain Graphene.
The presoma that the present invention is obtained to this comparative example has carried out transmission electron microscope detection (TEM), as a result as shown in figure 8, Fig. 8
The TEM figures of the presoma obtained for comparative example of the present invention 1；As seen from Figure 8, the presoma that this comparative example is obtained is medicine ball
Structure.
The Graphene that the present invention is obtained to this comparative example has carried out ESEM detection (SEM), as a result as shown in figure 9, Fig. 9
The SEM figures of the Graphene obtained for comparative example of the present invention 1；
The Graphene that the present invention is obtained to this comparative example has carried out transmission electron microscope detection (TEM), as a result as shown in Figure 10, figure
10 is the TEM figures of the Graphene that comparative example of the present invention 1 is obtained.Can be seen that what comparative example of the present invention 1 was obtained by Fig. 9 and Figure 10
Lamella pattern of the grapheme material for fold, but lamella is thicker, and degree of graphitization is relatively low.
The above is only the preferred embodiment of the present invention, it is noted that for the ordinary skill people of the art
For member, under the premise without departing from the principles of the invention, some improvements and modifications can also be made, these improvements and modifications also should
It is considered as protection scope of the present invention.
Claims (7)
1. a kind of preparation method of Graphene, comprises the following steps：
A) biological material, anion surfactant, hydrofluoric acid and water are mixed, hydro-thermal reaction is carried out, is obtained presoma, institute
The temperature for stating hydro-thermal reaction is 150～250 DEG C, and the time of the hydro-thermal reaction is 1～24 hour；The hydrofluoric acid it is mole dense
Spend for 0.01～2mol/L；During the biological material includes glucose, sucrose, fructose, sorbose, galactolipin and mannose
One or more；
B) by metallic catalyst and step A) presoma that obtains mixes, and obtains the presoma containing metallic catalyst；Institute
State one or more that metallic catalyst includes in molysite, ferrous salt, nickel salt and cobalt salt；
C) by step B) presoma containing metallic catalyst that obtains heated, and obtains Graphene.
2. preparation method according to claim 1, it is characterised in that the anion surfactant includes dodecyl
One or more in sodium sulphate, dodecyl sodium sulfate, neopelex and odium stearate.
3. preparation method according to claim 1, it is characterised in that the biological material is lived with the anionic surface
Property agent mass ratio be (10～50)：1.
4. preparation method according to claim 1, it is characterised in that the metallic catalyst and step A) obtain
The mass ratio of presoma is (0.01～1)：1.
5. preparation method according to claim 1, it is characterised in that step C) in heating temperature be 800～
1200℃；
The time of the heating is 1～5 hour.
6. preparation method according to claim 1, it is characterised in that step A) presoma that obtains is hollow chou
Structure, the thickness of the hollow ball spherical shell is 2～30nm.
7. the preparation method according to claim 1～6 any one, it is characterised in that step C) specifically include：Will
Pore creating material and step B) presoma containing metallic catalyst that obtains mixes, heated, obtain Graphene；
The pore creating material includes the one kind in water vapour, potassium hydroxide, potassium oxide, zinc chloride, phosphoric acid, sodium oxide molybdena and NaOH
Or it is several；
The pore creating material and step A) in biological material mass ratio be (1～5)：1.
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| KR20170117454A (en) * | 2015-02-13 | 2017-10-23 | 카본스케이프 리미티드 | Manufacture of graphite from biomass |
| CN104925796B (en) * | 2015-06-24 | 2017-03-15 | 上海大学 | A kind of preparation method of porous class grapheme material |
| CN104934238A (en) * | 2015-06-25 | 2015-09-23 | 东南大学 | Method for preparing porous graphene electrode material by air bubble template process and application of method |
| CN105060289B (en) * | 2015-09-21 | 2017-12-01 | 中南大学 | A kind of method that few layer graphene is prepared based on biomass waste material |
| CN106732405A (en) * | 2016-12-29 | 2017-05-31 | 大连理工大学 | A kind of method for preparing biomass-based Graphene fragment and the method for preparing adsorbent with its modification inorganic material |
| CN106335898B (en) * | 2016-08-23 | 2019-01-25 | 福建中禾新材料有限公司 | A kind of preparation method of graphene |
| CN106315568B (en) * | 2016-08-23 | 2019-01-11 | 深圳智裳科技有限公司 | A kind of preparation method of graphene |
| CN107265435A (en) * | 2017-06-29 | 2017-10-20 | 湖南科技大学 | Preparation method of surface micropore carbon hollow ball a kind of of graphene interlayers and products thereof |
| EP3820815A4 (en) * | 2018-07-09 | 2022-04-20 | Log 9 Materials Scientific Private Limited | System and method for synthesizing graphene supported photocatalytic nanomaterials for air purification |
| CN109399615B (en) * | 2018-11-27 | 2022-06-07 | 天津科技大学 | Preparation method of 3D-graphene material with biomass resource as carbon source |
| CN111825078B (en) * | 2019-04-22 | 2021-12-10 | 南京大学 | Method for preparing three-dimensional graphene foam material |
| CN111484002B (en) * | 2020-04-17 | 2023-06-09 | 南京动量材料科技有限公司 | Preparation method and application of porous graphene film |
| CN111470495B (en) * | 2020-04-24 | 2023-05-12 | 山东龙力生物科技股份有限公司 | Raw material for preparing graphene and method for preparing graphene by using raw material |
| CN111533112B (en) * | 2020-06-08 | 2023-06-06 | 江苏华夏制漆科技有限公司 | Graphene nano hollow sphere and preparation method thereof |
| CN112591740A (en) * | 2020-12-17 | 2021-04-02 | 华中科技大学 | Preparation method of graphene |
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