CN106365158A - Preparation method of graphene oxide, and preparation method of boron-doped reduced graphene oxide - Google Patents
Preparation method of graphene oxide, and preparation method of boron-doped reduced graphene oxide Download PDFInfo
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Abstract
The invention discloses a preparation method of graphene oxide, and a preparation method of boron-doped reduced graphene oxide. The preparation method of the graphene oxide is an improved method for preparing graphene oxide based on a Hummer technology, and provides a specific graphene oxide raw material for subsequent preparation of boron-doped reduced graphene oxide. The preparation method of the boron-doped reduced graphene oxide allows the boron-doped reduced graphene oxide to be obtained only through processing a graphene oxide and boric acid mixture solution for about 3-10 min under normal-temperature and normal-pressure conditions by using a dielectric barrier discharge plasma technology. Compared with traditional chemical vapor deposition and hydrothermal reaction methods, the preparation methods disclosed in the invention have the advantages of simple process, low cost, greenness and environmental protection, high efficiency and low energy consumption.
Description
Technical field
The invention belongs to the preparing technical field of Graphene associated materials is and in particular to a kind of preparation side of graphene oxide
Method and a kind of preparation method of boron-doping redox graphene.
Background technology
Grapheme material is a kind of two-dimentional honeycomb lattice structure being made up of carbon carbon hexatomic ring, due to its special heat conduction
And chemical property, superior mechanical performance, good optical property and higher specific surface area and obtain extensive concern.
It should be noted that grapheme material has prospect due to its higher electron mobility most as ultracapacitor
One of material.Make ortho position point that defect to occur because redox graphene CHARGE DISTRIBUTION is uneven after boron-doping, these defects can
To be effectively promoted the electric charge transfer between neighbouring carbon atom, the electrochemistry of boron-doping redox graphene therefore can be improved
Can be so as to be used widely in terms of ultra-capacitor.
There is many research to concentrate in the method preparing boron-doped graphite alkene at present, and have suitable achievement in some aspects,
The common method preparing boron-doped graphite alkene has: chemical vapor deposition, hydro-thermal reaction method.Using chemical vapour deposition technique, with benzene boron
Acid has successfully prepared monolayer boron-doped graphite alkene for presoma.Using hydro-thermal reaction, its body is graphene oxide and nabh4,
Achieve the boron element doping of Graphene, and and tio2Compound, significantly improve tio2Photocatalysis performance.But above-mentioned two
Kind of method, requires to Preparation equipment that higher and complex operation, response time length, efficiency are low；Its energy consumption is even more huge, also can cause
The pollution of environment；Boron-doping redox graphene can not be efficiently synthesized.
In addition, for the preparation method of graphene oxide, mainly have three kinds: a brodie method, staudenmaier method and
Hummers method.Wherein the preparation process of hummers method ageing relatively preferably and also also compare safety in preparation process, because
This is one kind the most frequently used at present.But the shortcoming of traditional hummers method is to produce toxic gas in preparation process
no2、n2o4Deng gas, these gases cause very big harm to atmospheric environment.
Content of the invention
Present invention aim to address in prior art, the complex process of synthesis boron-doping redox graphene, high energy consumption,
Response time length, efficiency are low, and the problems such as pollute environment and provide a kind of preparation method of graphene oxide, and the method can
There is provided a kind of graphene oxide of modified model hummers method preparation for preparation boron-doping redox graphene.
Employed technical scheme comprise that such for realizing the object of the invention, a kind of preparation method of graphene oxide, bag
Include following steps:
1.1) graphite powder is added to equipped with the first container of mixed acid solution, the first container is placed in ice-water bath, stirring,
Obtain the first black suspension a；Sulfuric acid solution that described mixed acid solution is 98% by concentration and the boric acid solution that concentration is 85%
Mixing composition, and the volume ratio (ml ml) of sulfuric acid solution and boric acid solution is 10 1～1 1, described graphite powder and mixed acid
The mass volume ratio (g ml) of solution is 1 500～5 500；The temperature of described ice-water bath is 0～20 DEG C；
1.2) potassium permanganate powder gradation is added in the first container that above-mentioned first black suspension a is located, obtains second
Black suspension b；The mass volume ratio (g ml) of described potassium permanganate powder and the first black suspension a is 10 400～10
500；
1.3) by step 1.2) in after the second black suspension b of obtaining is heated to 25～80 DEG C, be stirred, obtain black or
Pitchy suspension c；
1.4) by step 1.3) in the black that obtains or pitchy suspension c be cooled to after room temperature, in the first container successively plus
Enter deionized water, 30% hydrogenperoxide steam generator, 1mol l-1Hydrochloric acid solution, obtain yellowish-brown suspension d, described black or black
Brown suspension c, the volume ratio of deionized water, hydrogenperoxide steam generator and hydrochloric acid solution are 400 300 10 50；
1.5) by step 1.4) in the yellowish-brown suspension d that obtains carry out deionized water wash, Centrifugal dispersion, obtain sepia or
Pitchy precipitate e；
1.6) by step 1.5) in the sepia that obtains or pitchy precipitate e be vacuum dried under constant temperature, obtain
Graphene oxide.
It is further: in step 1.1) in, described stir speed (S.S.) is 400～800r/min, and described mixing time is 30
～60min.
It is further: in step 1.2) in, in the gradation adding procedure to potassium permanganate powder, add Gao Meng every time
The amount of sour potassium is 0.5～2 g；
In step 1.3) in, the speed of described stirring is 400～800r/min；The time of described stirring is 24～48h；
In step 1.5) in, after described deionized water wash process repeats 8～15 times, carry out Centrifugal dispersion；
In step 1.6) in, the temperature of described constant temperature is 35～100 DEG C；The described vacuum drying time is 12～24 h.
The preparation method of the graphene oxide described in the invention described above, its be improve on the basis of hummer method after
The method preparing graphene oxide, it can be for subsequently carrying out the preparation of boron-doping redox graphene and providing specific aoxidizing stone
Black alkene raw material, because such graphene oxide adopts boric acid to replace the sodium nitrate (nano in traditional hummer method3), therefore can subtract
Discharge toxic and harmful in few Graphene boron-doping preparation technology, the non-boron element of introducing can be reduced simultaneously as far as possible.
In addition, the present invention also provides a kind of preparation method of boron-doping redox graphene, comprise the steps:
2.1) graphene oxide and boric acid powder are added to equipped with the second container of deionized water, stir, obtain sepia
Suspension f, the mass ratio (g g) of described graphene oxide and boric acid is 1:1～3:1, described graphene oxide and deionized water
Mass volume ratio (g ml) be 1 200～1 500；
2.2) by step 2.1) in the sepia suspension f that obtains be vacuum dried under constant temperature, obtain lamellar forerunner
Body g；
2.3) by step 2.2) in the lamellar presoma g that obtains be placed in dielectric barrier discharge reactor, and in normal temperature and pressure bar
Under part, plasma treatment is carried out 3～10 minutes to lamellar presoma g, obtain sample h；
2.4) by step 2.3) in the sample h that obtains carry out washing, be vacuum dried, obtain boron-doping redox graphene.
It is further: in step 2.1) in, the speed of described stirring is 400～800r/min, the time of described stirring
For 30～60min.
It is further: in step 2.2) in, the temperature of described constant temperature is 35～100 DEG C；Described drying time is 6～12
h.
It is further: in above-mentioned steps 2.3) in, carry out being passed through to dielectric barrier discharge reactor during plasma treatment
80 v, the alternating current of 1.6 a.
It is further: in step 2.4) in, the second that described washing process is respectively adopted deionized water and concentration is 99.7%
Alcohol is washed；Described vacuum drying temperature is 35～100 DEG C, and the vacuum drying time is 4～12 h.
It is further: described dielectric barrier discharge reactor is with h2Quartz tube reactor as source of the gas.
Be further: in above-mentioned steps 2.1) used in graphene oxide be oxidation described in the invention described above
The preparation method of Graphene prepares gained.
The preparation method of the boron-doping redox graphene described in the invention described above, it is under normal temperature and pressure conditionses using Jie
Matter barrier discharge plasma technology processes the mixture solution of graphene oxide and boric acid, and only need to process about 3～10 minutes
Can get boron-doping redox graphene.Due to ionizing the free radical of generation under plasma conditions, gone using free radical
Capture oxygen-derived free radicals, after doping hetero atom, CHARGE DISTRIBUTION is uneven makes ortho position point defect, and these defects can effectively promote
Enter the electric charge transfer between neighbouring carbon atom；And, the addition of boron atom can make sp2 hydridization become apparent from.
The preparation method of the boron-doping redox graphene in the present invention is except adopting common graphene oxide system
Graphene oxide that is standby outer, also preferably being prepared using the preparation method of graphene oxide of the present invention, its advantage
It is the introducing that can reduce to non-boron element.
The preparation method of boron-doping redox graphene of the present invention is anti-with respect to traditional chemical vapor deposition, hydro-thermal
For answering method, there are process is simple, low cost, environmental protection, efficiency high, low power consumption and other advantages；And, can also lead in theory
Cross interpolation and obtain, containing other heteroatomic raw materials, multiple heteroatomic redox graphenes that adulterate.
Brief description
Fig. 1 is graphene oxide, redox graphene, the X-ray diffraction pattern of boron-doping redox graphene；
Fig. 2 is graphene oxide, redox graphene, the infrared figure of Fourier of boron-doping redox graphene；
Fig. 3 is graphene oxide, redox graphene, the Raman spectrogram of boron-doping redox graphene；
Fig. 4 is the scanning electron microscope (a) of boron-doping redox graphene, transmission electron microscope (b), high power transmission electron microscope (c) spectrogram.
Specific embodiment
With reference to embodiment, the invention will be further described, but only should not be construed the above-mentioned subject area of the present invention
It is limited to following embodiments.Without departing from the idea case in the present invention described above, according to ordinary skill knowledge and used
With means, make various replacements and change, all should include within the scope of the present invention.
Embodiment 1: prepare graphene oxide (go) (1)
1.1) graphite powder commercially available for 3g is added to equipped with the first container of mixed acid, the first container is placed in ice-water bath
Row stirring, obtains the first black suspension a；Wherein stirring can adopt magnetic agitation；
Sulfuric acid solution that above-mentioned mixed acid is 98% by 360ml concentration and the boric acid solution that 40ml concentration is 85% form, both sulphuric acid
The volume ratio (ml ml) of solution and boric acid solution is 9:1；The speed of described stirring is set to 500r/min；Described stirring when
Between be set to 30min；
The mass volume ratio (g ml) of above-mentioned graphite powder and mixed acid solution is about 3:400；
1.2) 10g potassium permanganate powder gradation is added in the first container that the first black suspension a is located, obtains second black
Color suspension b；Both the mass volume ratio (g ml) of potassium permanganate powder and the first black suspension a was about 10:400；And,
The amount adding potassium permanganate every time is 1 g；
1.3) by step 1.2) in after the second black suspension b of obtaining is heated to 35 DEG C, be stirred, obtain black or dark brown
Color suspension c；Wherein stirring can adopt magnetic agitation, and the speed of described stirring is set to 500r/min；Described stirring
Set of time is 48h；
1.4) by step 1.3) in the black that obtains or pitchy suspension c be cooled to after room temperature, in the first container successively plus
Enter 300ml deionized water, 10ml 30% hydrogenperoxide steam generator, 50ml 1mol l-1Hydrochloric acid solution, obtain yellowish-brown suspended
Liquid d；
1.5) by step 1.4) in yellow-brownish solution d that obtains carry out deionized water wash, Centrifugal dispersion, obtain sepia or black
Tan precipitate e；Wherein, after deionized water wash process is repeated 8 times, then carry out Centrifugal dispersion；
1.6) by step 1.5) in the sepia that obtains or pitchy precipitate e be vacuum dried under 35 DEG C of constant temperatures
24h, obtains graphene oxide.
Embodiment 2: prepare graphene oxide (go) (2)
1.1) graphite powder commercially available for 3g is added to equipped with the first container of mixed acid, the first container is placed in ice-water bath
Row stirring, obtains the first black suspension a；Wherein stirring can adopt magnetic agitation；
Sulfuric acid solution that above-mentioned mixed acid is 98% by 300ml concentration and the boric acid solution that 100ml concentration is 85% form, both sulphuric acid
The volume ratio (ml ml) of solution and boric acid solution is 3:1；The speed of described stirring is set to 600r/min；Described stirring when
Between be set to 45min；
The mass volume ratio (g ml) of above-mentioned graphite powder and mixed acid solution is about 3:400；
1.2) 8g potassium permanganate powder gradation is added in the first container that the first black suspension a is located, obtains second black
Color suspension b；Both the mass volume ratio (g ml) of potassium permanganate powder and the first black suspension a was about 10:500；And,
The amount adding potassium permanganate every time is 1 g；
1.3) by step 1.2) in after the second black suspension b of obtaining is heated to 50 DEG C, be stirred, obtain black or dark brown
Color suspension c；Wherein stirring can adopt magnetic agitation, and the speed of described stirring is set to 800r/min；Described stirring
Set of time is 35h；
1.4) by step 1.3) in the black that obtains or pitchy suspension c be cooled to after room temperature, in the first container successively plus
Enter 300ml deionized water, 10ml 30% hydrogenperoxide steam generator, 50ml 1mol l-1Hydrochloric acid solution, obtain yellowish-brown suspended
Liquid d；
1.5) by step 1.4) in yellow-brownish solution d that obtains carry out deionized water wash, Centrifugal dispersion, obtain sepia or black
Tan precipitate e；Wherein, after deionized water wash process is repeated 10 times, then carry out Centrifugal dispersion；
1.6) by step 1.5) in the sepia that obtains or pitchy precipitate e be vacuum dried under 80 DEG C of constant temperatures
12h, obtains graphene oxide.
General, the graphene oxide obtaining in above-described embodiment 1 and embodiment 2 is usually the graphene oxide of lamellar.
Afterwards, can first the graphene oxide of lamellar be reused after milled processed is for graphene oxide powder.In addition, if any must
Will, only need to be on the basis of above-described embodiment 1,2 after adjusting corresponding parameter, you can obtain more embodiments.
Embodiment 3: preparation boron-doping redox graphene (b-rgo) (1)
2.1) graphene oxide obtaining in above-described embodiment 1 is weighed 200mg and 100mg boric acid powder to be added to equipped with 50ml
In the second container of deionized water, stir 30min, obtain sepia suspension f；Wherein stirring can adopt magnetic agitation；Described
The speed of stirring is set to 400r/min；
2.2) by step 2.1) in the sepia suspension f that obtains carry out being vacuum dried 6h under 35 DEG C of constant temperature, obtain
Lamellar presoma g；
2.3) by step 2.2) in the lamellar presoma g that obtains be placed in dielectric barrier discharge reactor, and this dielectric impedance is put
Electric reactor is with h2Quartz tube reactor as source of the gas；Under normal temperature and pressure conditionses, it is passed through 80 v, the alternating current of 1.6 a
After plasma treatment is carried out 3 minutes to lamellar presoma g；Obtain sample h；
2.4) by step 2.3) in after the sample h that obtains carries out washing, is vacuum dried, obtain boron-doping redox graphene；Institute
Stating washing process is first to be washed using deionized water, then is washed using the ethanol that concentration is 99.7%；Described vacuum is done
Dry temperature is 35 DEG C；Drying time is 4 h.
Embodiment 4: preparation boron-doping redox graphene (b-rgo) (2)
2.1) graphene oxide obtaining in above-described embodiment 1 is weighed 150mg and 150mg boric acid powder to be added to equipped with 50ml
In the second container of deionized water, stir 30min, obtain sepia suspension f；Wherein stirring can adopt magnetic agitation；Described
The speed of stirring is set to 600r/min；
2.2) by step 2.1) in the sepia suspension f that obtains carry out being vacuum dried 6h under 65 DEG C of constant temperature, obtain
Lamellar presoma g；
2.3) by step 2.2) in the lamellar presoma g that obtains be placed in dielectric barrier discharge reactor, and this dielectric impedance is put
Electric reactor is with h2Quartz tube reactor as source of the gas；Under normal temperature and pressure conditionses, it is passed through 80 v, the alternating current of 1.6 a
After plasma treatment is carried out 5 minutes to lamellar presoma g；Obtain sample h；
2.4) by step 2.3) in after the sample h that obtains carries out washing, is vacuum dried, obtain boron-doping redox graphene；Institute
Stating washing process is first to be washed using deionized water, then is washed using the ethanol that concentration is 99.7%；Described vacuum is done
Dry temperature is 65 DEG C；Drying time is 6h.
Above-described embodiment 3 is that the graphene oxide directly adopting preparation in embodiment 1 prepares boron-doping oxygen reduction as raw material
Graphite alkene；Graphene oxide that alternate manner prepare may also be employed in theory as raw material.In addition, if it is necessary, only
Need to be on the basis of above-described embodiment 3,4 after adjusting corresponding parameter, you can obtain more embodiments.
Comparative example 5: prepare redox graphene (rgo)
2.1) graphene oxide obtaining in above-described embodiment 1 is weighed 200mg and be added to equipped with 50ml deionized water second
In container, stir 30min, obtain sepia suspension f；Wherein stirring can adopt magnetic agitation；The speed setting of described stirring
For 400r/min；
2.2) by step 2.1) in the sepia suspension f that obtains carry out being vacuum dried 6h under 35 DEG C of constant temperature, obtain
Lamellar presoma g；
2.3) by step 2.2) in the lamellar presoma g that obtains be placed in dielectric barrier discharge reactor, and this dielectric impedance is put
Electric reactor is with h2Quartz tube reactor as source of the gas；Under normal temperature and pressure conditionses, it is passed through 80 v, the alternating current of 1.6 a
After plasma treatment is carried out 3 minutes to lamellar presoma g；Obtain sample h；
2.4) by step 2.3) in after the sample h that obtains carries out washing, is vacuum dried, obtain boron-doping redox graphene；Institute
Stating washing process is first to be washed using deionized water, then is washed using the ethanol that concentration is 99.7%；Described vacuum is done
Dry temperature is 35 DEG C；Drying time is 4 h.
Above-described embodiment 3 and embodiment 5 are comparative examples, the two in addition to whether adding boric acid powder and having any different, its
The addition of excess product should be consistent as far as possible, to obtain optimal comparing result.In addition, if it is necessary, only need to be above-mentioned
On the basis of embodiment 3 and embodiment 5 after adjusting corresponding parameter, you can obtain more comparative examples.
Experimental example interpretation of result:
Go in Fig. 1, Fig. 2, Fig. 3 is the graphene oxide of preparation in embodiment 1, and rgo is the reduction-oxidation of preparation in embodiment 5
Graphene, b-rgo is the boron-doping redox graphene of preparation in embodiment 3.
Fig. 1 is graphene oxide, redox graphene, the X-ray diffraction spectrogram of boron-doping redox graphene
(xrd).
As can be seen from Figure 1 the characteristic peak (001) of go is about at 10.8 °, and this characteristic peak in rgo and b-rgo
Almost be wholly absent, this show presoma oxy radical plasma treated after basic being removed, in figure rgo and b-rgo
There is a wider peak (not having other derivative peaks) at 24.5 ° about places, show go reduction, be stripped.
Fig. 2 is graphene oxide, redox graphene, Fourier's infrared spectrum of boron-doping redox graphene.
It can be seen that the corresponding peak of oxygen-containing functional group of rgo and b-rgo lacks from the infrared spectrum of Fig. 2, this result
Consistent with the result of the xrd of Fig. 1.
Fig. 3 is graphene oxide, redox graphene, the Raman spectrogram of boron-doping redox graphene.
It can be seen in figure 3 that the d peak (about 1343cm-1) of sample and g peak (about 1580 cm-1), go, rgo and b-rgo
D peak, g peak (id/ig) strength ratio be respectively as follows: 1.22,0.96,0.89, show sample in the sp2 after corona treatment
Hydridization becomes apparent from, and the sp2 hydridization of b-rgo becomes apparent from, and mainly due to the introducing of boron atom, the defective bit of Graphene is accounted for
According to.
Fig. 4 is the scanning electron microscope (a) of boron-doping redox graphene, transmission electron microscope (b), high power transmission electron microscope (c) spectrogram；
Boron-doping redox graphene is made up of undulatory, fold thin slice as can be seen from Figure 4, and this pattern can carry
For a high open-celled structure, this structure can make electrolyte be more easy to enter each lamella, is conducive to electron transmission.
Claims (10)
1. a kind of preparation method of graphene oxide it is characterised in that: comprise the steps:
1.1) graphite powder is added to equipped with the first container of mixed acid solution, the first container is placed in ice-water bath, stirring,
Obtain the first black suspension a, the sulfuric acid solution that described mixed acid solution is 98% by concentration and the boric acid solution that concentration is 85%
Mixing composition, and the volume ratio (ml ml) of sulfuric acid solution and boric acid solution is 10 1～1 1, described graphite powder and mixed acid
The mass volume ratio (g ml) of solution is 1 500～5 500；The temperature of described ice-water bath is 0-20 DEG C；
1.2) potassium permanganate powder gradation is added in the first container that above-mentioned first black suspension a is located, obtains second
Black suspension b, the mass volume ratio (g ml) of described potassium permanganate powder and the first black suspension a is 10 400～20
1000；
1.3) by step 1.2) in after the second black suspension b of obtaining is heated to 25～80 DEG C, be stirred, obtain black or
Pitchy suspension c；
1.4) by step 1.3) in the black that obtains or pitchy suspension c be cooled to after room temperature, in the first container successively plus
Enter deionized water, 30% hydrogenperoxide steam generator, 1mol l-1Hydrochloric acid solution, obtain yellowish-brown suspension d, described black or black
Brown suspension c, the volume ratio of deionized water, hydrogenperoxide steam generator and hydrochloric acid solution are 400 300 10 50；
1.5) by step 1.4) in the yellowish-brown suspension d that obtains carry out deionized water wash, Centrifugal dispersion, obtain sepia or
Pitchy precipitate e；
1.6) by step 1.5) in the sepia that obtains or pitchy precipitate e be vacuum dried under constant temperature, obtain
Graphene oxide.
2. boron-doping redox graphene as claimed in claim 1 preparation method it is characterised in that: in step 1.1) in,
Described stir speed (S.S.) is 400～800r/min, and described mixing time is 30～60min.
3. boron-doping redox graphene as claimed in claim 1 or 2 preparation method it is characterised in that:
In step 1.2) in, in the gradation adding procedure to potassium permanganate powder, the amount of adding every time potassium permanganate is 0.5～
2 g；
In step 1.3) in, the speed of described stirring is 400～800r/min；The time of described stirring is 24～48h；
In step 1.5) in, after described deionized water wash process repeats 8～15 times, carry out Centrifugal dispersion；
In step 1.6) in, the temperature of described constant temperature is 35～100 DEG C；The described vacuum drying time is 12～24 h.
4. a kind of preparation method of boron-doping redox graphene it is characterised in that: comprise the steps:
2.1) graphene oxide powder and boric acid powder are added to equipped with the second container of deionized water, stir, obtain palm fibre
Brown suspension f, the mass ratio (g g) of described graphene oxide and boric acid is 1:1～3:1, described graphene oxide and go from
The mass volume ratio (g ml) of sub- water is 1 200～1 500；
2.2) by step 2.1) in the sepia suspension f that obtains be vacuum dried under constant temperature, obtain lamellar forerunner
Body g；
2.3) by step 2.2) in the lamellar presoma g that obtains be placed in dielectric barrier discharge reactor, and in normal temperature and pressure bar
Under part, plasma treatment is carried out 3～10 minutes to lamellar presoma g, obtain sample h；
2.4) by step 2.3) in the sample h that obtains carry out washing, be vacuum dried, obtain boron-doping redox graphene.
5. boron-doping redox graphene as claimed in claim 4 preparation method it is characterised in that: in step 2.1) in,
The speed of described stirring is 400～800r/min, and the time of described stirring is 30～60min.
6. boron-doping redox graphene as claimed in claim 4 preparation method it is characterised in that: in step 2.2) in,
The temperature of described constant temperature is 35～100 DEG C；Described drying time is 6～12 h.
7. boron-doping redox graphene as claimed in claim 4 preparation method it is characterised in that: in step 2.3) in,
Carry out during plasma treatment, being passed through the alternating current of 80 v, 1.6 a to dielectric barrier discharge reactor.
8. boron-doping redox graphene as claimed in claim 4 preparation method it is characterised in that: in step 2.4) in,
The ethanol that described washing process is respectively adopted deionized water and concentration is 99.7% is washed；Described vacuum drying temperature is
35～100 DEG C, the vacuum drying time is 4～12 h.
9. boron-doping redox graphene as claimed in claim 4 preparation method it is characterised in that: described dielectric impedance is put
Electric reactor is with h2Quartz ampoule plasma reactor as source of the gas.
10. the boron-doping redox graphene as any one of claim 4 to 9 preparation method it is characterised in that:
Step 2.1) in, the graphene oxide being used is the preparation side of the graphene oxide any one of claims 1 to 3
Method prepares gained.
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| Publication number | Priority date | Publication date | Assignee | Title |
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