CN109231190A - Prepare redox graphene method and its redox graphene obtained - Google Patents
Prepare redox graphene method and its redox graphene obtained Download PDFInfo
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Abstract
The present invention provides a kind of method for preparing redox graphene, and graphite oxide is carried out first time microwave radiation, cooling, and graphite oxide after cooling is carried out second of microwave radiation.The invention further relates to a kind of redox graphenes, are prepared by the above method.The method provided by the invention for preparing redox graphene, which handles graphite oxide by microwave radiation mode twice, can efficiently prepare the redox graphene of the high reduction degree of high-specific surface area.
Description
Technical field
The present invention relates to field of nanometer material technology, in particular to a kind of method for preparing redox graphene and its
Redox graphene obtained.
Background technique
Graphene in the outstanding representation of the aspect of performance such as light, electricity, heat, power due to making it in biological medicine, energy storage, light
The fields such as electro-catalysis, space flight and aviation, equipment protection are widely studied and applied.Currently, successively having developed four class bases
This preparation method, including mechanical stripping, chemical vapor deposition, epitaxial growth, redox.In these four types of methods, oxidation is also
Former method is considered most industrial since production cost is relatively low, is not necessarily to special installation and the advantages such as production process is simple
Change one of the method for productive potentialities.But there is reduction journey in the redox graphene that current oxidation-reduction method is prepared
Spend the problems such as low and specific surface area is too small.
Summary of the invention
The present invention provides a kind of method for preparing redox graphene, can efficiently prepare the reduction of high-specific surface area height
The redox graphene of degree.
The present invention provides a kind of redox graphene, has the characteristics that high-specific surface area and high reduction degree.
The present invention is achieved through the following technical solutions above-mentioned purpose.
In a first aspect, the embodiment of the present invention provides a kind of method for preparing redox graphene, graphite oxide is carried out
First time microwave radiation, it is cooling, graphite oxide after cooling is subjected to second of microwave radiation.
Second aspect, the embodiment of the present invention provide a kind of redox graphene, are prepared into using above-mentioned preparation method
It arrives.
The method provided by the invention for preparing redox graphene and redox graphene, pass through microwave radiation twice
Graphite oxide is handled, the efficiency that traditional microwave method up-stripping graphite oxide obtains redox graphene is effectively improved,
Improve the reduction degree and specific surface area of redox graphene.
The aspects of the invention or other aspects can more straightforwards in the following description.
Detailed description of the invention
Fig. 1 is the optical microscope photograph for the graphite oxide that the embodiment of the present invention 1 provides.
Fig. 2 is the optical microscope photograph for the redox graphene that the embodiment of the present invention 1 provides.
Fig. 3 is the specific surface area N for the redox graphene that the embodiment of the present invention 1 provides2Adsorption/desorption isothermal curve figure.
Fig. 4 is the XPS analysis figure for the redox graphene that the embodiment of the present invention 1 provides.
Specific embodiment
It in order to make the object, technical scheme and advantages of the embodiment of the invention clearer, below will be in the embodiment of the present invention
Technical solution be clearly and completely described.The person that is not specified actual conditions in embodiment, according to normal conditions or manufacturer builds
The condition of view carries out.Reagents or instruments used without specified manufacturer is the conventional production that can be obtained by commercially available purchase
Product.
Redox graphene refers to one kind by carbon atom with sp2Hybridized orbit forms the two dimension that hexangle type is in honeycomb lattice
Carbon nanomaterial is in black, as shown in Fig. 2, redox graphene has excellent optics, electricity, mechanical characteristic, in material
, micro-nano technology, the energy, biomedicine and drug delivery etc. are with important application prospects, and redox graphene can
To be made by graphite oxide, for example, a part of oxygen-containing functional group of graphite oxide is restored to obtain.
Graphite oxide also known as graphite oxide or graphitic acid are a kind of carbon indefinite by the ratio between the amount of substance, hydrogen, oxygen element
The compound of composition.Graphite oxide can handle graphite preparation, carbon, the oxygen object of the higher product of degree of oxidation by strong oxidizer
The ratio between amount of matter is a kind of yellow solid between 2.1 to 2.9, and still retains the main body layer structure of graphite, but specific fine
Structure becomes more sophisticated.Graphite oxide is changed into the process of redox graphene in addition to the reduction for being related to oxygen-containing functional group is anti-
It answers, further relates to the process that a kind of graphite oxide of unswollen state is removed to the redox graphene for single layer.Microwave radiation
The oxygen-containing functional group on its surface is set to be broken down into gas by heated oxide graphite, the pressure that gas generates overcomes piece interlayer
Van der Waals force, redox graphene are successfully removed.
As one aspect of the present invention, the application provides a kind of method for preparing redox graphene, including following
Step: graphite oxide is prepared.
In certain embodiments of the present invention, graphite oxide can be prepared by following manner: by crystalline flake graphite and
Sodium nitrate is added to the container, and it is 0 DEG C that the reaction vessel, which is placed in temperature, after the concentrated sulfuric acid that addition weight percent concentration is 98%
Ice-water bath in, be stirred to react, the reaction time for example controls in 30min or more, is added to potassium permanganate as oxidant
In said vesse, continue to be stirred to react, the reaction time is, for example, 1h or more, and after reaction is completed, which is transferred to
In water bath, bath temperature is for example controlled at 35 DEG C, continues to be stirred to react, and is stirred 30min, distilled water is then added, by this
Container is transferred in 98 DEG C of oil bath, is continued to stir 15min, is sequentially added distilled water and H2O2Solution, H2O2The quality of solution point
Numerical example for example 30%.In reaction system finally at glassy yellow after, filter to obtain graphite oxide.It, can be by above-mentioned reaction after filtering
Graphite oxide obtained is washed with hydrochloric acid to improve the purity of graphite oxide.When washing, hydrochloric acid volume: graphite weight is
(450~800) ml:1g, such as 500ml:1g, 600ml:1g, 700ml:1g are dry after washing.
In other some embodiments, graphite oxide can also be prepared in the following manner: by crystalline flake graphite and
K2S2O8、P2O5It being added in 98% concentrated sulfuric acid, heating reaction, temperature is for example controlled at 80 DEG C, and the reaction time controls in 6h or more,
After be cooled to room temperature, diluted, be washed out to neutrality with distilled water, dry, the graphite oxide pre-oxidized, obtained by weighing
Pre-oxidation graphite be added in 98% concentrated sulfuric acid, under the conditions of 0 DEG C of ice-water bath, be added oxidant such as potassium permanganate, reaction
For example under the conditions of 35 DEG C, the reaction time controls in such as 2h or more temperature.Pair of distilled water and 30% is added after reaction
Oxygen water, is filtered while hot, pickling.When washing, hydrochloric acid volume: graphite weight be (450~800) ml:1g, as 500ml:1g,
600ml:1g, 700ml:1g etc. are dry after washing.
In other some embodiments, graphite oxide can also be prepared in the following manner:
The concentrated nitric acid of 98% concentrated sulfuric acid and 68% is added to the container, is stirred to react, the reaction time for example controls
Crystalline flake graphite is slowly added into the reaction vessel by 15min or more, and after being stirred to react, potassium chlorate is added, it is anti-to continue stirring
It answers, the reaction time for example controls in 96h or more, is diluted with distilled water, filters, pickling.When washing, hydrochloric acid volume: graphite weight
Amount is (450~800) ml:1g, such as 500ml:1g, 600ml:1g, 700ml:1g, drying after washing.
Graphite oxide is prepared in oxidation-reduction method compared with the existing technology by using quantitative salt acid elution graphite oxide
The generation that can avoid spent acid waste water to the full extent is washed to neutral mode with a large amount of hydrochloric acid solutions and deionized water afterwards, is had
Conducive to industrialized production.In addition to this, oxidized graphite flake interlayer can be subjected to displacement phenomenon during a large amount of water and salt acid elution,
It is unfavorable for subsequent microwave method reduction removing graphite oxide.
The graphite oxide being prepared is subjected to first time microwave radiation.It is understood that in some embodiments,
Graphite oxide can use commercial product.
In certain embodiments of the present invention, the power of first time microwave radiation be 600~820w, such as 700w,
730w, 760w, 800w etc..In some embodiments, first time microwave radiation can also using constant power microwave into
Row, such as during first time microwave radiation, first radiated using the power of 700W, after radiated time t, by microwave power
It increases to 800W or 600W is reduced to be radiated.
Since graphite oxide is conductive, under microwave action, huge eddy current can be generated inside graphite oxide, is produced
Raw violent heating effect, makes the oxygen-containing functional group being inserted into graphite oxide sharply decompose and volatilize, and acutely expand, and realizes layer
Between removing.Microwave irradiation power influences the reaction rate that graphite oxide carries out reduction reaction.Microwave power is too low, reduction reaction
Speed is too slow, is unfavorable for efficiently preparing redox graphene.In certain power bracket, power is higher, reduction reaction into
Capable speed is faster, is more than the power bracket, and partial oxidation of graphite can be broken by calcination.First time microwave radiation in the present invention
Power be 600~820w, such as 700w, 730w, 760w, 800w can avoid graphite oxide while guaranteeing reaction speed
Fault rupture.
In certain embodiments of the present invention, microwave radiation can carry out in the microwave equipments such as micro-wave oven, for the first time
The time of microwave radiation is 20~55s, such as 25s, 30s, 40s, 50s.
Microwave radiation processing graphite oxide with the reaction time lengthening, graphite oxide expansion process be divided into two ranks
Section, the volume of first stage graphite oxide can increase with the lengthening of radiated time, and second stage is in microwave irradiation time mistake
When long, partial oxidation of graphite can be broken by calcination, and the volume of graphite oxide can gradually become smaller.First time microwave spoke in the present invention
The time penetrated is 20~55s, such as 25s, 30s, 40s, 50s, ensure that graphite oxide reached bigger degrees of expansion and
It is not in calcination phenomenon.It when microwave power is larger, can suitably reduce the microwave time, to prevent in prolonged microwave spoke
It penetrates down, graphite oxide internal temperature is excessively high and generates calcination phenomenon and destroys layer structure.Such as microwave power be 600-700W
When, the adjustable microwave time is 40-55s；When microwave power is 700-820w, the adjustable microwave time is 20-50s.
After first time microwave radiation, graphite oxide is cooled down.
In certain embodiments of the present invention, the cooling time be 2~11min, such as 5min, 6min, 7min,
8min,9min.Graphite oxide internal temperature constantly increases during first time microwave radiation, existing in order to avoid generating calcination
As carrying out 2~11min, such as the cooling of 5min, 6min, 7min, 8min, 9min after first time microwave radiation.Specific behaviour
Make to be, for example, that graphite oxide is placed in the temperature for making it internal under room temperature to be reduced to room temperature (15-35 DEG C), to guarantee to aoxidize
Graphite keeps stable state after carrying out certain volume expansion.In some embodiments it is possible to which graphite oxide is received
Appearance cooled down in microwave equipment, such as: when carrying out first time microwave radiation, by graphite oxide be placed in micro-wave oven into
Row, after first time microwave radiation, graphite oxide is rested in micro-wave oven, is added conducive to the residual temperature in micro-wave oven
Heat improves the reducing degree of graphite oxide so that reduction reaction persistently carries out, and the raising of reducing degree can reduce micro- for the second time
The time of wave radiation.
Graphite oxide after cooling is subjected to second of microwave radiation.
In certain embodiments of the present invention, the power of second of microwave radiation be 600~820W, such as 700W,
730W,760W,800W.In some embodiments, second of microwave radiation can also be carried out using the microwave of constant power,
Such as during second of microwave radiation, is first radiated using the power of 700W, after radiated time t, microwave power is increased
It adds to 800W or 600W is reduced to be radiated.Second of microwave power can be made different according to the power of first time microwave
Adjustment.In some embodiments, it has been realized in after using high power such as 800W microwave treatment 55s for the first time to oxidation stone
The height reduction of ink, the graphite oxide microwave absorption capacity after greatly improving reduction, therefore secondary microwave power can be with
It is corresponding to reduce or shorten the microwave time.
Microwave irradiation power influences the reaction rate that graphite oxide carries out reduction reaction.Microwave power is too low, reduction reaction
Speed is too slow, is unfavorable for efficiently preparing redox graphene.In certain power bracket, power is higher, reduction reaction into
Capable speed is faster, is more than the power bracket, and partial oxidation of graphite can be broken by calcination.Second of microwave radiation in the present invention
Power be 600~820w, such as 700w, 730w, 760w, 800w, avoid graphite oxide to break while guaranteeing reaction speed
It splits.
In certain embodiments of the present invention, microwave radiation can carry out in the microwave equipments such as micro-wave oven, and second
The time of microwave radiation is 20~55s, such as 25s, 30s, 40s, 50s.
Second of microwave radiation can make the graphite oxide further progress reduction reaction for reaching certain degrees of expansion, volume
Further expansion, to advantageously form the redox graphene of single layer, improve redox graphene specific surface area and
Reduction degree.The mode of microwave radiation processing graphite oxide is relative to traditional microwave radiation oxygen reduction fossil of small-power twice
Ink can improve microwave irradiation power to a certain extent, substantially shorten the time of microwave radiation, effectively improve microwave method stripping
Efficiency from graphite oxide.The time of second of microwave radiation is 20~55s, such as 25s, 30s, 40s, 50s in the present invention, is protected
Graphite oxide has been demonstrate,proved to have reached bigger degrees of expansion and be not in calcination phenomenon.When microwave power is larger, Ke Yishi
When reducing the microwave time, to prevent under prolonged microwave radiation, graphite oxide internal temperature is excessively high and generates calcination phenomenon
Destroy layer structure.Such as when microwave power is 600-700W, the adjustable microwave time is 40-55s；Microwave power is
When 700-820w, the adjustable microwave time is 20-50s.
In other some embodiments, the graphite oxide after second of microwave radiation can also be carried out more
Microwave radiation.
Second aspect utilizes redox graphene obtained by the above method the present invention provides a kind of.The reduction-oxidation
Graphene has high specific surface area and high reduction degree.
In certain embodiments of the present invention, the specific surface area of redox graphene is 820~1340m2/ g, such as
1333m2/g、1001m2/g、820m2/ g etc., C/O atomic ratio are 12.5~20, such as 19,14.9,15.6 etc..High-specific surface area
There is good chemical property and dispersibility with the redox graphene of high reduction degree, can satisfy the application of different field
It is required that.
To sum up, compared with prior art, the invention has the following beneficial effects:
(1) efficiency that graphite oxide is removed in reduction process is effectively improved.
(2) resulting redox graphene is prepared with high specific surface area and high reduction degree, is shown good
Chemical property has dispersibility well, can satisfy the application requirement of different field.
(3) the method for the present invention is simple and efficient, and reduces the generation of spent acid waste water, greatly improves oxidation-reduction method preparation
The efficiency of graphene, is conducive to industrialized production.
Below in conjunction with specific embodiment to the method and redox graphene for preparing redox graphene of the invention
It is described in further detail.
Embodiment 1
It weighs 1g crystalline flake graphite and 0.5g sodium nitrate is placed in the round-bottomed flask of 250mL, measuring weight percent concentration is
98% concentrated sulfuric acid 23mL is added in the round-bottomed flask, and magneton is added, which is placed in 0 DEG C of ice-water bath, is stirred
30min is mixed, 3g potassium permanganate is weighed and is added in reactor, continues to stir 1h, reacts after completing, which is transferred to
In 35 DEG C of water-bath, continue to stir 30min, the distilled water for measuring 50mL is added in the round-bottomed flask, then burns the round bottom
Bottle is transferred in 98 DEG C of oil bath, continues to stir 15min, sequentially adds distilled water 140mL and mass fraction is 30%
H2O210mL, in reaction system finally at glassy yellow after, filtering, the hydrochloric acid 500mL for being 5%HCl with mass fraction washs, most
Whole product is placed in 50 DEG C of baking ovens dry 36h and obtains graphite oxide.
It weighs graphite oxide product made from the above method of 0.05g to be placed in 150mL flask, it is fixed to place the beaker 800W
In power household microwave oven, first microwave reaction 50s takes out the cooling 5min of beaker, places into continuation microwave 50s in micro-wave oven.
Embodiment 2
The crystalline flake graphite for weighing 2g is added to 3mL and contains 3gK2S2O8And 3gP2O598% concentrated sulfuric acid in, at 80 DEG C
Heat 6h, after be cooled to room temperature, diluted with distilled water, washing is dry to neutrality, and the graphite oxide pre-oxidized weighs institute
Obtained pre-oxidation graphite 1g is added in the concentrated sulfuric acid of 46mL, under the conditions of 0 DEG C of ice-water bath, 3g potassium permanganate is added, 35
Under the conditions of DEG C, 2h is reacted.46mL distilled water is added after reaction, slowly adds the distilled water of 280mL and pair of 5mL30% afterwards
Oxygen water, is filtered while hot, is finally washed with 5% dilute hydrochloric acid of 500mL, and final product is placed in 50 DEG C of baking ovens dry 36h.
The graphite oxide product prepared by the above method for weighing 0.05g is placed in 150mL flask, places the beaker 800W
Determine in power household microwave oven, first microwave reaction 50s, takes out the cooling 5min of beaker, place into continuation microwave 50s in micro-wave oven.
Embodiment 3
The concentrated sulfuric acid of 17.5mL98% and the concentrated nitric acid of 9mL68% are measured in the flask of 250mL, 15min is stirred, weighs
The crystalline flake graphite of 1g is slowly added into flask, and after stirring evenly, the potassium chlorate of 11g is added, and reacts 96h, dilute with the distilled water of 800mL
It releases, filters, washed with the dilute hydrochloric acid of 500mL 5%, final graphite oxide product is placed in 50 DEG C of baking oven dry 36h.
The graphite oxide product prepared by the above method for weighing 0.05g is placed in 150mL flask, places the beaker 800W
Determine in power household microwave oven, first microwave reaction 50s, takes out the cooling 5min of beaker, place into continuation microwave 50s in micro-wave oven.
Embodiment 4
The graphite oxide product being made by embodiment 1 for weighing 0.05g is placed in 150mL flask, places the beaker 600W
Determine in power household microwave oven, first microwave reaction 50s, takes out the cooling 5min of beaker, place into continuation microwave 50s in micro-wave oven.
Embodiment 5
The graphite oxide product being made by embodiment 1 for weighing 0.05g is placed in 150mL flask, places the beaker 700W
Determine in power household microwave oven, first microwave reaction 50s, takes out the cooling 5min of beaker, place into continuation microwave 50s in micro-wave oven.
Embodiment 6
The graphite oxide product being made by embodiment 1 for weighing 0.05g is placed in 150mL flask, places the beaker 800W
Determine in power household microwave oven, first microwave reaction 20s, takes out the cooling 5min of beaker, place into continuation microwave 20s in micro-wave oven.
Embodiment 7
The graphite oxide product being made by embodiment 1 for weighing 0.05g is placed in 150mL flask, places the beaker 800W
Determine in power household microwave oven, first microwave reaction 50s, takes out the cooling 10min of beaker, place into continuation microwave 50s in micro-wave oven.
Embodiment 8
The graphite oxide product being made by embodiment 1 for weighing 0.05g is placed in 150mL flask, places the beaker 800W
Determine in power household microwave oven, first microwave reaction 50s, takes out the cooling 2min of beaker, place into continuation microwave 50s in micro-wave oven.
Embodiment 9
The graphite oxide product being made by embodiment 1 for weighing 0.05g is placed in 150mL flask, places the beaker 700W
Determine in power household microwave oven, first microwave reaction 50s, take out the cooling 2min of beaker, places into power as 800W micro-wave oven relaying
Continuous microwave 50s.
Comparative example 1
The graphite oxide product as made from the first step for weighing 0.05g is placed in 150mL flask, and it is fixed to place the beaker 800W
In power household microwave oven, microwave reaction 100s.
Comparative example 2
It weighs 1g crystalline flake graphite and 0.5g sodium nitrate is placed in the round-bottomed flask of 250mL, measuring weight percent concentration is
98% concentrated sulfuric acid 23mL is added in the round-bottomed flask, and magneton is added, which is placed in 0 DEG C of ice-water bath, is stirred
30min is mixed, 3g potassium permanganate is weighed and is added in reactor, continues to stir 1h, reacts after completing, which is transferred to
In 35 DEG C of water-bath, continue to stir 30min, the distilled water for measuring 50mL is added in the round-bottomed flask, then burns the round bottom
Bottle is transferred in 98 DEG C of oil bath, continues to stir 15min, sequentially adds distilled water 140mL and mass fraction is 30%
H2O210mL, in reaction system finally at glassy yellow after, filtering, with a large amount of deionized waters wash until neutrality.
Graphite oxide aqueous solution 20ml, ultrasonic mixing 40min is taken to be completely dispersed graphene oxide in deionized water, obtain
To graphene oxide dispersion, graphene oxide dispersion 30ml is taken, 80 μ l of hydrazine hydrate is added, mass percent concentration is
26% ammonium hydroxide 0.5ml, deionized water 15ml, ultrasonic disperse 40min, solution after being dispersed, control pH value are 8~10.It will
Solution is placed in single neck flask after dispersion, is reacted 120min at a temperature of 90 DEG C, is obtained redox graphene dispersion liquid, mistake
It filters, be dried to obtain redox graphene powder.
Test example 1
Graphite oxide obtained in embodiment 1 and redox graphene are imaged under an optical microscope, respectively such as Fig. 1
And shown in Fig. 2, wherein as can be seen from Figure 1 graphite oxide is in glassy yellow in appearance, and redox graphene is in black.
By redox graphene made from embodiment 1-9 and comparative example 1-2 according to shown in " GB/T 19587-2004 "
Test method, according to N2BET principle measurement the specific area is adsorbed, XPS (x-ray photoelectron is used under the conditions of room temperature low fluorine
Energy disperse spectroscopy) measurement C/O atomic ratio, Fig. 3 is the specific surface area N for the redox graphene that embodiment 1 is prepared2Adsorption/desorption
Isothermal curve figure, Fig. 4 is the XPS analysis figure for the redox graphene that embodiment 1 is prepared, according to specific surface area N2Absorption
Desorption isothermal curve figure and XPS analysis figure can analyze to obtain the specific surface area of redox graphene and C/O atomic ratio, equally
Method pair
The test result of embodiment 2-9 and comparative example 1-2 are analyzed, and result such as table 1 is analyzed.
The specific surface area and C/O atomic ratio of 1 redox graphene of table
| Embodiment | Specific surface area m2/g | C/O atomic ratio |
| Embodiment 1 | 1333 | 19.0 |
| Embodiment 2 | 1211 | 15.6 |
| Embodiment 3 | 1001 | 18.1 |
| Embodiment 4 | 821 | 12.7 |
| Embodiment 5 | 927 | 16.3 |
| Embodiment 6 | 1190 | 14.9 |
| Embodiment 7 | 1288 | 19.6 |
| Embodiment 8 | 1150 | 13.2 |
| Embodiment 9 | 980 | 15.0 |
| Comparative example 1 | 378 | 11.2 |
| Comparative example 2 | 58 | 8.2 |
The data comparison of embodiment 1-9 and comparative example 1-2 can be seen that twice that microwave treatment graphite oxide can from table 1
To significantly improve the specific surface area and C/O atomic ratio of product redox graphene.Specifically, embodiment 1-9 is by micro- twice
The numberical range of the specific surface area for the redox graphene that wave processing graphite oxide obtains is 821-1333m2/ g, C/O atom
The range of ratio is 12.7-19.6, and the ratio table for the redox graphene that a microwave treatment graphite oxide obtains in comparative example 1
Area is 378m2/ g, C/O atomic ratio are 11.2, the reduction-oxidation graphite obtained in comparative example 2 using traditional reduction-oxidation method
The specific surface area of alkene is 58m2/ g, C/O atomic ratio are 8.2, and the mode of microwave treatment graphite oxide twice can be obtained by, which comparing, at least may be used
The specific surface area of product redox graphene is improved into 443m2/ g, C/O atomic ratio improve 1.5.
The data result of embodiment 1-9, which can be seen that, in contrast table 1 is arranged different microwave irradiation powers, first time microwave
The oxygen reduction for radiating and different specific surface areas and difference C/O atomic ratio capable of being obtained second of microwave irradiation time, cooling time
Graphite alkene.In the range of 600-820w, microwave irradiation power is higher, then for first time microwave radiation and second of microwave radiation
The specific surface area and C/O atomic ratio of obtained redox graphene are higher.In addition to this, within the scope of 20~55s, for the first time
Microwave radiation is directlyed proportional to the specific surface area of redox graphene and C/O atomic ratio to second of microwave irradiation time.It is cold
But the time influences the specific surface area of redox graphene and C/O atomic ratio little.
Embodiments described above is a part of the embodiment of the present invention, instead of all the embodiments.Reality of the invention
The detailed description for applying example is not intended to limit the range of claimed invention, but is merely representative of selected implementation of the invention
Example.Based on the embodiments of the present invention, obtained by those of ordinary skill in the art without making creative efforts
Every other embodiment, shall fall within the protection scope of the present invention.
Claims (10)
1. a kind of method for preparing redox graphene, which is characterized in that first time microwave radiation is carried out to graphite oxide, it is cold
But, second of microwave radiation is carried out to the graphite oxide after cooling.
2. the method for preparing redox graphene as described in claim 1, which is characterized in that the first time microwave radiation
Power be 600~820w, preferably 700~820w.
3. the method for preparing redox graphene as claimed in claim 2, which is characterized in that the first time microwave radiation
Time be 20~55s, preferably 30~50s.
4. the method for preparing redox graphene as described in claim 1, which is characterized in that second of microwave radiation
Power be 600~820w, preferably 700~820w.
5. the method for preparing redox graphene as claimed in claim 4, which is characterized in that second of microwave radiation
Time is 20~55s, preferably 30~50s.
6. the method for preparing redox graphene as described in claim 1, which is characterized in that the time of the cooling is 2
~11min, preferably 5~7min.
7. as described in claim 1 prepare redox graphene method, which is characterized in that the graphite oxide by with
Under type preparation: graphite, sodium nitrate being mixed, insulation reaction in acid condition, mix insulation reaction with potassium permanganate, with
Water, H2O2Successively hybrid reaction.
8. the method for preparing redox graphene as claimed in claim 7, which is characterized in that further include to described in acquisition
The step of graphite oxide is washed with hydrochloric acid, the hydrochloric acid volume: graphite weight is (450~800) ml:1g, is done after washing
It is dry.
9. a kind of redox graphene, which is characterized in that be prepared into using method as described in any one of claims 1 to 8
It arrives.
10. redox graphene as claimed in claim 9, which is characterized in that the specific surface of the redox graphene
Product is 820~1340m2/ g, C/O atomic ratio are 12.5~20.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113735103A (en) * | 2021-09-30 | 2021-12-03 | 昆明理工大学 | Method for rapidly preparing large graphene sheets in large scale |
| CN114682210A (en) * | 2020-12-30 | 2022-07-01 | 中国科学院理化技术研究所 | Hierarchical pore graphene and preparation method and application thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20080048152A1 (en) * | 2006-08-25 | 2008-02-28 | Jang Bor Z | Process for producing nano-scaled platelets and nanocompsites |
| CN102107870A (en) * | 2011-03-23 | 2011-06-29 | 中国科学院山西煤炭化学研究所 | Method for quickly preparing reduced graphene by using microwaves |
| CN105645381A (en) * | 2016-01-12 | 2016-06-08 | 山东联星能源集团有限公司 | Method for preparing graphene/carbon nanotube composite material by intensive microwave process |
| CN107673340A (en) * | 2017-11-22 | 2018-02-09 | 肇庆中特能科技投资有限公司 | Graphene and preparation method thereof |
| CN108358191A (en) * | 2018-05-10 | 2018-08-03 | 郑州新世纪材料基因组工程研究院有限公司 | A kind of low defect graphene and preparation method thereof |
-
2018
- 2018-11-02 CN CN201811303532.7A patent/CN109231190A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20080048152A1 (en) * | 2006-08-25 | 2008-02-28 | Jang Bor Z | Process for producing nano-scaled platelets and nanocompsites |
| CN102107870A (en) * | 2011-03-23 | 2011-06-29 | 中国科学院山西煤炭化学研究所 | Method for quickly preparing reduced graphene by using microwaves |
| CN105645381A (en) * | 2016-01-12 | 2016-06-08 | 山东联星能源集团有限公司 | Method for preparing graphene/carbon nanotube composite material by intensive microwave process |
| CN107673340A (en) * | 2017-11-22 | 2018-02-09 | 肇庆中特能科技投资有限公司 | Graphene and preparation method thereof |
| CN108358191A (en) * | 2018-05-10 | 2018-08-03 | 郑州新世纪材料基因组工程研究院有限公司 | A kind of low defect graphene and preparation method thereof |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114682210A (en) * | 2020-12-30 | 2022-07-01 | 中国科学院理化技术研究所 | Hierarchical pore graphene and preparation method and application thereof |
| CN114682210B (en) * | 2020-12-30 | 2024-02-20 | 中国科学院理化技术研究所 | Hierarchical porous graphene and preparation method and application thereof |
| CN113735103A (en) * | 2021-09-30 | 2021-12-03 | 昆明理工大学 | Method for rapidly preparing large graphene sheets in large scale |
| CN113735103B (en) * | 2021-09-30 | 2022-09-16 | 昆明理工大学 | Method for rapidly preparing large graphene sheets in large scale |
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