CN108439379A - A kind of preparation method for the porous graphene nano material that aperture is controllable - Google Patents
A kind of preparation method for the porous graphene nano material that aperture is controllable Download PDFInfo
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 120
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 119
- 239000002086 nanomaterial Substances 0.000 title claims abstract description 43
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 claims abstract description 62
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical group [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000000725 suspension Substances 0.000 claims abstract description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 11
- 238000002604 ultrasonography Methods 0.000 claims abstract description 10
- 239000011787 zinc oxide Substances 0.000 claims abstract description 10
- 150000003839 salts Chemical class 0.000 claims abstract description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000002253 acid Substances 0.000 claims description 9
- 229910002804 graphite Inorganic materials 0.000 claims description 7
- 239000010439 graphite Substances 0.000 claims description 7
- 239000012153 distilled water Substances 0.000 claims description 5
- 238000010828 elution Methods 0.000 claims description 5
- -1 graphite alkene Chemical class 0.000 claims description 5
- 239000001301 oxygen Substances 0.000 claims description 5
- 229910052760 oxygen Inorganic materials 0.000 claims description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 4
- 238000005406 washing Methods 0.000 claims description 2
- 239000011148 porous material Substances 0.000 abstract description 9
- 238000001035 drying Methods 0.000 abstract description 8
- 230000002950 deficient Effects 0.000 abstract description 5
- 238000004519 manufacturing process Methods 0.000 abstract description 4
- 150000003751 zinc Chemical class 0.000 abstract description 4
- 239000000203 mixture Substances 0.000 abstract 1
- 238000012512 characterization method Methods 0.000 description 15
- 239000000463 material Substances 0.000 description 11
- 238000000034 method Methods 0.000 description 11
- 230000005540 biological transmission Effects 0.000 description 6
- 238000002484 cyclic voltammetry Methods 0.000 description 5
- 238000009826 distribution Methods 0.000 description 5
- 238000001069 Raman spectroscopy Methods 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 230000007547 defect Effects 0.000 description 4
- 230000002328 demineralizing effect Effects 0.000 description 4
- 238000001228 spectrum Methods 0.000 description 4
- 150000001336 alkenes Chemical class 0.000 description 3
- 238000004090 dissolution Methods 0.000 description 3
- 230000005611 electricity Effects 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 239000011259 mixed solution Substances 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 238000000643 oven drying Methods 0.000 description 3
- 239000004575 stone Substances 0.000 description 3
- 238000000967 suction filtration Methods 0.000 description 3
- 239000003990 capacitor Substances 0.000 description 2
- 239000003575 carbonaceous material Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 235000013399 edible fruits Nutrition 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000007772 electrode material Substances 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 238000010884 ion-beam technique Methods 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 238000010923 batch production Methods 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000010894 electron beam technology Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000003628 erosive effect Effects 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
- C01B32/182—Graphene
- C01B32/184—Preparation
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/24—Electrodes characterised by structural features of the materials making up or comprised in the electrodes, e.g. form, surface area or porosity; characterised by the structural features of powders or particles used therefor
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
- H01G11/32—Carbon-based
- H01G11/36—Nanostructures, e.g. nanofibres, nanotubes or fullerenes
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2204/00—Structure or properties of graphene
- C01B2204/04—Specific amount of layers or specific thickness
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2204/00—Structure or properties of graphene
- C01B2204/20—Graphene characterized by its properties
- C01B2204/22—Electronic properties
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- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2204/00—Structure or properties of graphene
- C01B2204/20—Graphene characterized by its properties
- C01B2204/32—Size or surface area
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/13—Energy storage using capacitors
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Abstract
It is graphene oxide ultrasonic disperse to be formed into graphene oxide suspension in water, then mix with nearly saturation zinc nitrate solution, continuing ultrasound makes it be uniformly mixed the invention discloses a kind of preparation method for the porous graphene nano material that aperture is controllable；It filters so that graphene oxide and zinc nitrate are trapped on filter paper, and cover one layer of defective zinc salt template in surface of graphene oxide；Then load there is into the drying of the filter paper of graphene oxide and zinc nitrate, it is placed in Muffle furnace and burns, exposed graphene oxide outside completely burned in the high temperature environment in defective hole, it is zinc oxide that zinc nitrate thermally decomposes in the high temperature environment, and porous graphene is successfully obtained after removing zinc oxide using hydrochloric acid.The present invention can obtain the porous graphene nano material of different pore size by the control to ignition temperature, time and salt amount in Muffle furnace, to considerably reduce the manufacturing cost of porous graphene, improve utilization ratio.
Description
Technical field
The present invention relates to controllable porous in a kind of preparation method of porous graphene nano material more particularly to a kind of aperture
The preparation method of graphene nano material.
Background technology
Graphene is a kind of novel carbon material that latest developments are got up, and has open band gap, super large specific surface
Product, high mechanical properties.However, graphene is reunited since the effect of π-pi-electron is easy to generate so as to cause effective ratio area
It declines to a great extent.Derivative of the porous graphene as graphene, the hole in material be carbon atom be removed from lattice or
Person is transferred to surface and the vacancy that leaves, and the introducing in hole has not only well solved the shortcomings that graphene is easily reunited, in property
The characteristics of energy aspect also well combines graphene and porous carbon, good electric conductivity and chemical stability allow it to protect
High charge capacity is held, has in energy stores and conversion field and has big application prospect, is graphene band structure and electricity
The regulation and control of performance create new path.
Currently, the method for preparing porous graphene nano material mainly has high energy ion beam blast technique, template and chemistry
The methods of etching, aperture are difficult to control, it is also difficult to realize batch production.In addition, these existing synthetic methods all exist
Itself inevitable defect, these defects directly limit certain special applications.Such as it is straight with electron beam, helium ion beam etc.
The method that the surface of bombardment graphene obtains porous graphene is connect, a very high energy source is needed, it could be in graphene table
Face produces pore space structure, this also means that higher cost and energy expenditure.For template, either template is carved
Erosion or template growth, although large-scale pore structure manufacture may be implemented in this method, pore size can also obtain preferably
Control, but the preparation process of itself is cumbersome, and the residual of mould material is a unavoidable problem.Therefore, urgently
A kind of method for preparing porous graphene that is more efficient, cheap, pure and being capable of volume production of demand.
Invention content
The purpose of the present invention is to provide a kind of preparation methods for the porous graphene nano material that aperture is controllable.
The method that the present invention prepares porous graphene nano material is that graphene oxide ultrasonic disperse is formed oxygen in water
Graphite alkene suspension, then mixed with nearly saturation zinc nitrate solution, continuing ultrasound makes it be uniformly mixed；It filters so that oxidation stone
Black alkene and zinc nitrate are trapped on filter paper；Then load there is into the drying of the filter paper of graphene oxide and zinc nitrate, is placed in Muffle
It burns in stove complete, products therefrom first uses salt acid elution to remove zinc oxide, then is washed with distilled water demineralizing acid；After washing completely
Product is dried to get porous graphene nano material.
The preparating mechanism of the present invention：Graphene is water-dispersed mixed with nearly saturation zinc nitrate solution after through suction filtration so that oxygen
Graphite alkene and zinc nitrate are trapped on filter paper, and cover one layer of defective zinc salt template in surface of graphene oxide；Combustion
When burning, in defective hole exposed graphene oxide outside in the high temperature environment with oxygen the reaction was complete burning, zinc nitrate is in height
Thermal decomposition is zinc oxide in warm environment, and being reduced removal by its functional group of graphene oxide that zinc oxide covers becomes graphene.
After zinc oxide being removed using hydrochloric acid after burning completely successfully obtain porous graphene.
One layer of defective zinc salt template is covered since suction filtration process needs to be oxidized graphene surface, if zinc nitrate is dense
Degree is too small, and suction filtration process cannot form the defect template of endless all standing, therefore need to control graphene oxide and zinc nitrate
Mass ratio is 1:200~1:1200.
A concentration of 1 ~ 5 g/L of the graphene oxide suspension.Ignition temperature in the Muffle furnace is 400 DEG C ~ 550
DEG C, burning time is 1min ~ 10min.
Fig. 1 is the phenogram of porous graphene nano material prepared by the present invention, and wherein A is Raman Characterization；B is
XRD characterization；C is the full spectrum of XPS characterizations；D is the C1s spectrums of XPS characterizations.Raman Characterization result can see, porous graphite
There are three apparent Raman peaks for alkene tool, and the peaks D of wherein graphene are considered as caused by defect, and expression is SP3Carbon it is former
Son；G bands are graphene E2gThe characteristic peak of vibration, expression is SP2Carbon atom；The peaks 2D indicate that graphene is multilayer.It calculates
IG/I2D values are more than 1.8, show that graphene number of plies is more than 5 layers according to document.XRD characterization the result shows that, graphene is in 2 θ
There is diffraction maximum at 24.5 °, the diffraction maximum position consistency with graphite in document, but diffraction maximum wideization, this is because stone
Caused by ink sheet interlamellar spacing reduces, the integrality of crystal structure declines, the degree of disorder increases.XPS characterization results show porous graphene
In it is very weak with the relevant peak intensity of carbon-oxygen bond, and with C-C（284.6 eV）Relevant peak occupies leading position, shows to aoxidize stone
Black alkene has been reduced to graphene.
Fig. 2 is the electrical property characterization of porous graphene nano material prepared by the present invention, and wherein A is cyclic voltammetry
As a result；B is galvanostatic charge/discharge measurement result.The present invention has investigated the electrical property of prepared porous graphene material, this hair
The highest specific capacity that bright prepared porous graphene material is obtained is 290 F/g, far above the ratio of graphene in document
138 F/g of capacity（Chen et al. 2010）, illustrate that the material has good capacitance characteristic.Cyclic voltammetry curve shape connects
Nearly rectangle shows excellent capacitance characteristic and rate capability.For ideal electrode material, at electrode/electrolyte interface
Electric double layer can be quickly and evenly formed, when the moment that voltage scanning direction changes, electric current can be rapidly reached stable state, therefore its
Cyclic voltammetry curve shows as rectangle.For general carbon material electrode, due to the presence of decentralized capacitance effect, i.e. decentralized capacitance
Ohmic voltage is resulted in hole electrolyte inside resistance to decline, when rapidly changing voltage scanning direction, electric current needs certain
Time can be only achieved stable state, its cyclic voltammetry curve is caused to deviate ideal rectangular shape.Constant current charge-discharge curve shows electricity
Pressure is linearly increased or reduced substantially as charge and discharge, shows its quick I-V response.Ultracapacitor or electrode
An important feature be to quick charge and discharge, it is therefore desirable to high service life, i.e. cyclical stability.The present invention
Prepared porous graphene material is after cycle 500 times, and the specific capacity of capacitor keeps 98%, after recycling 5000 times, still
The specific capacity for maintaining 83% shows good performance.
In conclusion the present invention, using zinc salt as template, the one-step method for realizing porous graphene is quickly prepared, and by right
The porous graphene nano material of different pore size can be obtained in the control of the amount of ignition temperature, time and the zinc nitrate of addition, from
And the manufacturing cost of porous graphene is considerably reduced, improve utilization ratio.The introducing in hole can effectively prevent graphene film
Again it stacks, high charge capacity is made to be maintained, to make up deficiency of the graphene as electrode material for super capacitor, make
It has great application with good electric conductivity, in energy storage field.
Description of the drawings
Fig. 1 is the phenogram of porous graphene nano material prepared by the present invention, and wherein A is Raman Characterization；B is
XRD characterization；C is the full spectrum of XPS characterizations；D is the C1s spectrums of XPS characterizations；
Fig. 2 is the electrical property characterization of porous graphene nano material prepared by the present invention, and wherein A is cyclic voltammetry knot
Fruit；B is galvanostatic charge/discharge measurement result；
Fig. 3 is the transmission electron microscope table of the porous graphene nano material prepared by 1 minute of burning under the different ignition temperatures of embodiment 1
Sign figure, wherein A are 400 DEG C；B is 450 DEG C；C is 500 DEG C；D is 550 DEG C；
Fig. 4 is that burn under the different ignition temperatures of embodiment 1 pore-size distribution of the porous graphene nano material prepared by 1 minute is united
Meter is as a result, wherein A is 400 DEG C；B is 450 DEG C；C is 500 DEG C；D is 550 DEG C；
Fig. 5 is the transmission electron microscope phenogram of prepared porous graphene nano material under the conditions of the different burning times of embodiment 2,
Wherein A is 450 DEG C and burns 1 minute；B is 450 DEG C and burns 10 minutes；
Fig. 6 is the pore-size distribution statistics knot of prepared porous graphene nano material under the conditions of the different burning times of embodiment 2
Fruit, wherein A are 450 DEG C and burn 1 minute；B is 450 DEG C and burns 10 minutes；
Fig. 7 is embodiment 3 in different graphenes：The transmission electricity of prepared porous graphene nano material under zinc nitrate mass ratio
Mirror phenogram, wherein A are 1:200；B is 1:600；C is 1:1200；
Fig. 8 is embodiment 3 in different graphenes：The aperture point of prepared porous graphene nano material under zinc nitrate mass ratio
Cloth statistical result, wherein A are 1:200；B is 1:600；C is 1:1200.
Specific implementation mode
The preparation method and performance of the porous graphene nano material of different pore size are made below by specific embodiment
It further illustrates.
Embodiment 1, different time condition burning prepare porous graphene nano material
（1）200 mL of graphene oxide suspension of 5 g/L is configured, 3 h of room temperature ultrasound are spare；
（2）1 g zinc nitrates are weighed, after adding 3 mL water dissolutions, the graphene oxide suspension of 5 g/L of 1 mL is added thereto,
10 min of mixing ultrasound；
（3）Using Buchner funnel by step（2）Mixed solution filter to quantitative filter paper；
（4）There is the filter paper of graphene oxide and zinc nitrate to be put into 60 DEG C of drying of baking oven load；
（5）The temperature that Muffle furnace is set separately is 400 DEG C, 450 DEG C, 500 DEG C, 550 DEG C, will after furnace temperature rises to established temperature
Filter paper after drying is put into Muffle furnace, and product is taken out after the 1min that burns；
（6）Product after burning is first used into salt acid elution, after removing zinc oxide, then is washed with distilled water demineralizing acid；It has washed
Product is put into baking oven drying after complete, you can obtain the porous graphene of different pore size.
Fig. 3 is that burn under the different ignition temperatures transmission electron microscope of the porous graphene nano material prepared by 1 minute characterizes
Figure, wherein A are 400 DEG C；B is 450 DEG C；C is 500 DEG C；D is 550 DEG C.Fig. 4 is to burn 1 minute under corresponding different ignition temperatures
The pore-size distribution statistical result of prepared porous graphene nano material, wherein A are 400 DEG C；B is 450 DEG C；C is 500 DEG C；D
It is 550 DEG C.As can be seen from Figures 3 and 4 that when ignition temperature is 400 DEG C, the aperture of porous graphene nano material is 1.6 nm
Left and right；When ignition temperature is 450 DEG C, the aperture of porous graphene nano material is 2.6 nm or so；It is 500 in ignition temperature
DEG C when, the aperture of porous graphene nano material is 30.3 nm or so；When ignition temperature is 550 DEG C, porous graphene nanometer
The aperture of material is 51.8 nm or so.As described above, rising with heat treatment temperature, aperture gradually increases this phenomenon explanation
The formation in hole and heat treatment process are closely related.
In order to further illustrate the influence of temperature, the present invention selects porous prepared by 450 and 500 DEG C of two medium temperatures
Graphene has carried out specific surface area test, as shown in table 1：
Embodiment 2, different time condition burning prepare porous graphene nano material
（1）200 mL of graphene oxide suspension of 5 g/L is configured, 3 h of room temperature ultrasound are spare；
（2）1 g zinc nitrates are weighed, after adding 3 mL water dissolutions, the graphene oxide suspension of 5 g/L of 1 mL is added thereto,
10 min of mixing ultrasound；
（3）Using Buchner funnel by step（2）Mixed solution filter to quantitative filter paper；
（4）There is the filter paper of graphene oxide and zinc nitrate to be put into 60 DEG C of drying of baking oven load；
（5）The temperature of Muffle furnace is set as 450 DEG C, after furnace temperature rises to established temperature, the filter paper after drying is put into Muffle furnace,
It burns respectively and takes out product after 1 min, 10 min；
（6）Product after burning is first used into salt acid elution, after removing zinc oxide, then is washed with distilled water demineralizing acid；It has washed
Product is put into baking oven drying after complete, you can obtain the porous graphene of different pore size.
Fig. 5 and Fig. 6 is the transmission electron microscope of preparation-obtained porous graphene nano material under the conditions of different burning times
Characterization and pore-size distribution statistical result, wherein A are 450 DEG C and burn 1 minute that the aperture of the porous graphene nano material of preparation is
2.6 nm or so, B are 450 DEG C and burn 10 minutes that the aperture of the porous graphene nano material of preparation is 43.8 nm or so.Such as
Upper described, the growth of heat treatment time can make the aperture increases of porous graphene.Burning time be 450 DEG C 1 minute it is made
The specific surface area of standby porous graphene material is listed as 648 m2/g in embodiment 1, it is contemplated that burning time is 450 DEG C
The aperture of porous graphene material prepared by 10 minutes and 500 DEG C in the embodiment 1 porous graphene materials prepared by 1 minute
Aperture it is close, therefore there is no measurement the specific area to 450 DEG C of porous graphene materials prepared by 10 minutes.
Porous graphene nano material is prepared under embodiment 3, the graphene of different quality ratio, zinc nitrate
（1）200 mL of graphene oxide suspension of 5 g/L is configured, 3 h of room temperature ultrasound are spare；
（2）The zinc nitrate of 1 g, 3 g, 6 g are weighed respectively（Graphene is corresponded to respectively:The mass ratio 1 of zinc nitrate:200、1:600、
1:1200）, after adding 3 mL water dissolutions, the graphene oxide suspension of 5 g/L of 1 mL, mixing ultrasound is added thereto respectively
10 min；
（3）Using Buchner funnel by step（2）In mixed solution filter to quantitative filter paper；
（4）There is the filter paper of graphene oxide and zinc nitrate to be put into 60 DEG C of drying of baking oven load；
（5）The temperature of Muffle furnace is set as 450 DEG C, after furnace temperature rises to established temperature, the filter paper after drying is put into Muffle furnace,
Burn 1 min, takes out product；
（6）Product after burning is first used into salt acid elution, after removing zinc oxide, then is washed with distilled water demineralizing acid；It has washed
Product is put into baking oven drying after complete, you can obtain the porous graphene of different pore size.
Fig. 7 and Fig. 8 is the graphene of different quality ratio：Zinc nitrate under the conditions of certain ignition temperature prepared by obtain
Porous graphene nano material transmission electron microscope characterization and pore-size distribution statistical result, wherein A be 1:200；B is 1:600；C
It is 1:1200.Fig. 7 and Fig. 8 are shown, in graphene:Zinc nitrate is 1:When 200, the aperture of porous graphene nano material is 2.6
Nm or so；In graphene:Zinc nitrate is 1:When 600, the aperture of porous graphene nano material is 10.7 nm or so；In graphite
Alkene:Zinc nitrate is 1:When 1200, the aperture of porous graphene nano material is 18 nm or so.This otherness shows salt content
Raising can result in the increase in aperture.
Different graphenes:The specific surface area for the porous graphene nano material burnt under zinc nitrate prepared by 1 minute is such as
Shown in table 2：
Claims (4)
1. a kind of preparation method for the porous graphene nano material that aperture is controllable, it is characterised in that：By graphene oxide ultrasound
It is dispersed in water to form graphene oxide suspension, then is mixed with nearly saturation zinc nitrate solution, continuing ultrasound makes it be uniformly mixed；
It filters so that graphene oxide and zinc nitrate are trapped on filter paper；Then load is had to the filter of graphene oxide and zinc nitrate
Paper is dried, and is placed in Muffle furnace and is burnt completely, products therefrom first uses salt acid elution to remove zinc oxide, then is washed with distilled water removal
Hydrochloric acid；Product is dried to get porous graphene nano material after washing completely.
2. the preparation method of the controllable porous graphene nano material in aperture as described in claim 1, it is characterised in that：The oxygen
A concentration of 1 ~ 5 g/L of graphite alkene suspension.
3. the preparation method of the controllable porous graphene nano material in aperture as described in claim 1, it is characterised in that：The oxygen
The mass ratio of graphite alkene and zinc nitrate is 1:200~1:1200.
4. the preparation method of the controllable porous graphene nano material in aperture as described in claim 1, it is characterised in that：The horse
Not the ignition temperature in stove is 400 DEG C ~ 550 DEG C, and burning time is 1min ~ 10min.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109368621A (en) * | 2018-12-24 | 2019-02-22 | 中国科学院兰州化学物理研究所 | The method of porous graphene is directly prepared by graphite |
| CN112079349A (en) * | 2020-08-25 | 2020-12-15 | 中国科学院兰州化学物理研究所 | Method for preparing nitrogen-doped porous graphene nano material through limited-area combustion and application |
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| CN107619040A (en) * | 2017-11-01 | 2018-01-23 | 中国科学院兰州化学物理研究所 | The method that partial combustion method quickly prepares porous graphene |
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| CN107619040A (en) * | 2017-11-01 | 2018-01-23 | 中国科学院兰州化学物理研究所 | The method that partial combustion method quickly prepares porous graphene |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109368621A (en) * | 2018-12-24 | 2019-02-22 | 中国科学院兰州化学物理研究所 | The method of porous graphene is directly prepared by graphite |
| CN112079349A (en) * | 2020-08-25 | 2020-12-15 | 中国科学院兰州化学物理研究所 | Method for preparing nitrogen-doped porous graphene nano material through limited-area combustion and application |
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