CN110092372A - A kind of improved method preparing graphene oxide - Google Patents
A kind of improved method preparing graphene oxide Download PDFInfo
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- CN110092372A CN110092372A CN201910472609.1A CN201910472609A CN110092372A CN 110092372 A CN110092372 A CN 110092372A CN 201910472609 A CN201910472609 A CN 201910472609A CN 110092372 A CN110092372 A CN 110092372A
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- hydrogen peroxide
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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
- C01B32/198—Graphene oxide
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Abstract
The embodiment of the invention discloses a kind of improved methods for preparing graphene oxide, which comprises (1) in cold stage, potassium permanganate is slowly added in the mixture of the concentrated sulfuric acid and concentrated phosphoric acid mixed acid and graphite flake, is sufficiently reacted；(2) gains are continued to react in ice bath；(3) then gains are kept to 50 DEG C in oil bath；(4) gains are poured into ice, hydrogen peroxide is then added dropwise into ice and gains, obtain golden solution mixture.This method does not generate toxic and harmful gas during the preparation process；The high-temperature heating stage during the preparation process is eliminated, avoids and generates the danger such as unnecessary explosion, heat release；The amount that hydrogen peroxide is added during technique final process is also substantially reduced than the prior art.
Description
Technical field
The present invention relates to chemical preparation techniques fields, and in particular to a kind of improved method for preparing graphene oxide.
Background technique
Graphene is a kind of material being popular, and is widely used in the fields such as conductive, thermally conductive, catalysis.Since English in 2004
Since Geim and Novoselove the discovery single-layer graphene of state Manchester (Manchester) university, the side of graphene has been prepared
Method is more and more.Comprehensively consider preparation cost, it is that cost is relatively low, production phase that oxidation-reduction method, which prepares graphene oxide (GO),
To a kind of stable method.
It is Hummer oxidation-reduction method and its improved method that the method for preparing graphene oxide now, which is used most, generally
Reaction step be low temperature to be passed through, three medium temperature, high temperature reaction process, used compound generally comprises carbon dust, Gao Meng
Sour potassium (KMnO4), sodium nitrate (NaNO3), the concentrated sulfuric acid (H2SO4), concentrated nitric acid (HNO3), hydrogen peroxide (H2O2) etc., in some improvement
Method in also used phosphorus pentoxide (P2O5), concentrated phosphoric acid (H3PO4) etc..
In Hummer method, graphite flake is aoxidized into intercalation with oxidant when low temperature, oxidant tilts graphite flake edge,
It is aoxidized into inside；It is further aoxidized in medium temperature, makes the further separation of graphite flake layer distance；Finally pass through high temperature rank
Section, successfully prepares graphene oxide.But in this process, it will use NaNO3, concentrated nitric acid etc., the meeting in oxidation process
Generate toxic gas and a large amount of sour gas, can health on scientific research personnel and environment cause biggish injury and influence.Separately
Outside, in last handling process, hydrogen peroxide (H is added in general literature2O2) amount usually in 20mL or so, and in reaction process
In there is no document specifically to describe this kind of oxidation-reduction method to prepare during graphene oxide the phenomenon that occurring.
Summary of the invention
The embodiment of the present invention is designed to provide a kind of improved method for preparing graphene oxide.It is prepared by this method
Toxic and harmful gas is not generated in journey；The high-temperature heating stage during the preparation process is eliminated, it is unnecessary quick-fried to avoid generation
The danger such as fried, heat release；The amount that hydrogen peroxide is added during technique final process is also substantially reduced than the prior art.
To achieve the above object, the embodiment of the present invention provides a kind of improved method for preparing graphene oxide, the method
Include the following steps:
(1) in cold stage, by 9g potassium permanganate (KMnO4) it is slowly added to the excessive concentrated sulfuric acid (H of low temperature2SO4) and dense phosphorus
Acid (H3PO4) mixed acid and 1.5g graphite flake mixture in, sufficiently reacted；
(2) 30min is reacted into gains continuation in ice bath；
(3) then by gains 50 DEG C of holding 12h in oil bath；
(4) gains are poured into ice, hydrogen peroxide (H is then added dropwise into ice and gains2O2), it obtains golden yellow
Solution mixture；
(5) gained golden solution mixture is centrifuged, washed, is freeze-dried.
In step (1), after potassium permanganate adds, the color of mixture becomes blackish green from black, and not any
Gas generates；Solution becomes golden yellow after reaction.This method does not pass through pyroprocess, reduces during the reaction
Risk.
Further, in step (1), the volume ratio of the concentrated sulfuric acid and concentrated phosphoric acid is (8-10) in the mixed acid: 1.It is preferred that
The volume ratio of the concentrated sulfuric acid and concentrated phosphoric acid is 9:1 in the mixed acid.
Further, in step (1), the fineness of the graphite flake is 1000 mesh.
Further, reaction is made to keep exothermic temperature at 5 DEG C or less in step (1).
Further, reaction carries out 12 hours in step (1).
Further, in step (4), the amount that hydrogen peroxide is added is 3ml.
Further, step (5) specifically includes: gained golden solution mixture is centrifuged, and with after salt pickling,
It is washed with water to neutrality, is then freeze-dried.
The method of the present invention for the prior art generated present in the method for preparing graphene oxide (GO) toxic gas,
The risk of hot stage, addition hydrogen peroxide (H2O2) it is excessive the problems such as, improve the work that oxidation-reduction method prepares graphite oxide
Skill process, i.e., using being reacted in low temperature, the reaction time of thermophase in extension makes graphite in the further oxygen of middle thermophase
The method of change improves the technique for preparing graphene oxide, obtains better test effect.
The embodiment of the present invention has the advantages that
1, this method does not generate toxic and harmful gas during the preparation process；
2, the high-temperature heating stage during the preparation process is eliminated, avoids and generates the danger such as unnecessary explosion, heat release；
3, the amount that hydrogen peroxide is added during technique final process is also substantially reduced than the prior art.
Detailed description of the invention
It, below will be to embodiment party in order to illustrate more clearly of embodiments of the present invention or technical solution in the prior art
Formula or attached drawing needed to be used in the description of the prior art are briefly described.It should be evident that the accompanying drawings in the following description is only
It is merely exemplary, it for those of ordinary skill in the art, without creative efforts, can also basis
The attached drawing of offer, which is extended, obtains other implementation attached drawings.
Structure depicted in this specification, ratio, size etc., only to cooperate the revealed content of specification, for
Those skilled in the art understands and reads, and is not intended to limit the invention enforceable qualifications, therefore does not have technical
Essential meaning, the modification of any structure, the change of proportionate relationship or the adjustment of size are not influencing the function of the invention that can be generated
Under effect and the purpose that can reach, should all still it fall in the range of disclosed technology contents obtain and can cover.
Fig. 1 is the process flow diagram of the improved method provided in an embodiment of the present invention for preparing graphene oxide.
Wherein appended drawing reference are as follows:
1, cold stage reacts；2, ice bath reacts；3, medium temperature elementary reaction；4, hydrogen peroxide is added dropwise；
5, it is centrifuged；6, pickling；7, it washes；8, it is freeze-dried.
Specific embodiment
Embodiments of the present invention are illustrated by particular specific embodiment below, those skilled in the art can be by this explanation
Content disclosed by book is understood other advantages and efficacy of the present invention easily, it is clear that described embodiment is the present invention one
Section Example, instead of all the embodiments.Based on the embodiments of the present invention, those of ordinary skill in the art are not doing
Every other embodiment obtained under the premise of creative work out, shall fall within the protection scope of the present invention.
Embodiment 1
Referring to Fig. 1, it is shown that is provided in one embodiment of the invention prepares the work of the improved method of graphene oxide
Skill flow diagram.
The step of improved method of graphene oxide is prepared in the embodiment is as follows:
(1) in cold stage 1, by 9g potassium permanganate (KMnO4) it is slowly added to the excessive concentrated sulfuric acid (H of low temperature2SO4) and it is dense
Phosphoric acid (H3PO4) mixed acid (volume ratio 9:1) and 1.5g graphite flake (1000 mesh) mixture in, sufficiently reacted, instead
It should continue 12 hours, and reaction is made to keep exothermic temperature at 5 DEG C or less；After potassium permanganate adds, the color of mixture from
Black becomes blackish green, and generates without any gas；
(2) by the gains 30min that pours into ice bath that the reaction was continued, ice bath reaction 2 is carried out；
(3) then by gains 50 DEG C of holdings 12h in oil bath, progress medium temperature elementary reaction 3；
(4) gains are poured into ice, 3ml hydrogen peroxide (H is then added dropwise into ice and gains2O2) 4, obtain gold
Yellow solution mixture, and primary colors will not be become again；
(5) the golden solution mixture of step (4) is centrifuged 5, and with after salt pickling 6, being washed with water 7 to neutrality, then
Freeze-drying 8 is carried out, graphene oxide product is obtained.
The embodiment of the present invention generates during preparing graphene oxide (GO) without toxic and harmful gas.In low temperature loop order
Section is by potassium permanganate (KMnO4) be slowly added in mixed acid solution, keep exothermic temperature at 5 DEG C.Because potassium permanganate is added
(KMnO4) after the case where interlamellar spacing increasing should occur in the graphite oxide ideal that can generate a large amount of heat, and prepare, if put
Hot temperature is excessively high to will lead to raw graphite piece stacking, and oxidant not can be carried out intercalation oxidation, reaction is caused to fail.
The stage for reducing high-temperature heating during the preparation process avoids and generates the danger such as unnecessary explosion, heat release.One
As oxidation-reduction method can pass through 90 DEG C of hot stage, in the method for the embodiment of the present invention, extend medium temperature (50 DEG C) reaction time,
It avoids strong oxidizer to be heated in high temperature, to avoid danger.
Hydrogen peroxide (H is added during testing final process2O2) occur golden yellow afterwards, and primary colors will not be become again.Some
Improved oxidation-reduction method prepares the hydrogen peroxide (H that about 20ml can generally be added in the method for graphite oxide2O2), and in the present invention
In the method for embodiment, it is only necessary to 3ml hydrogen peroxide (H be added2O2), solution just will become golden yellow.
Although above having used general explanation and specific embodiment, the present invention is described in detail, at this
On the basis of invention, it can be made some modifications or improvements, this will be apparent to those skilled in the art.Therefore,
These modifications or improvements without departing from theon the basis of the spirit of the present invention are fallen within the scope of the claimed invention.
Claims (9)
1. a kind of improved method for preparing graphene oxide, which is characterized in that the method includes the following steps:
(1) in cold stage, 9g potassium permanganate is slowly added to the excessive concentrated sulfuric acid of low temperature and concentrated phosphoric acid mixed acid and 1.5g
In the mixture of graphite flake, sufficiently reacted；
(2) 30min is reacted into gains continuation in ice bath；
(3) then by gains 50 DEG C of holding 12h in oil bath；
(4) gains are poured into ice, hydrogen peroxide is then added dropwise into ice and gains, obtain golden solution mixing
Object；
(5) gained golden solution mixture is centrifuged, washed, is freeze-dried.
2. the method according to claim 1, wherein in step (1), the concentrated sulfuric acid and concentrated phosphoric acid in the mixed acid
Volume ratio be (8-10): 1.
3. according to the method described in claim 2, it is characterized in that, in step (1), the concentrated sulfuric acid and concentrated phosphoric acid in the mixed acid
Volume ratio be 9:1.
4. according to the method described in claim 2, it is characterized in that, the fineness of the graphite flake is 1000 mesh in step (1).
5. according to the method described in claim 4, it is characterized in that, in step (1), make reaction keep exothermic temperature 5 DEG C with
Under.
6. according to the method described in claim 5, being carried out 12 hours it is characterized in that, being reacted in step (1).
7. method according to claim 1 to 6, which is characterized in that in step (1), potassium permanganate addition is finished
Afterwards, the color of mixture becomes blackish green from black, and generates without any gas.
8. according to the method described in claim 6, it is characterized in that, the amount that hydrogen peroxide is added is 3ml in step (4).
9. the method according to claim 1, wherein step (5) specifically includes: gained golden solution is mixed
Object is centrifuged, and with after salt pickling, is washed with water to neutrality, is then freeze-dried.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102491318A (en) * | 2011-12-13 | 2012-06-13 | 河北工业大学 | Method for preparing graphene oxide |
| CN104556016A (en) * | 2015-01-23 | 2015-04-29 | 青岛科技大学 | Low-temperature environment-friendly preparation method of graphene |
| WO2015060782A1 (en) * | 2013-10-21 | 2015-04-30 | Hwv Technologies Pte. Ltd. | Graphene oxide/polymer composite membranes and methods of forming thereof |
| CN104860302A (en) * | 2015-04-28 | 2015-08-26 | 南京信息工程大学 | Preparation method of wide interlayer spacing and easily-striping graphite oxide |
| CN108069415A (en) * | 2018-01-18 | 2018-05-25 | 燕山大学 | A kind of preparation method of the graphene aerogel of size classification |
-
2019
- 2019-05-31 CN CN201910472609.1A patent/CN110092372A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102491318A (en) * | 2011-12-13 | 2012-06-13 | 河北工业大学 | Method for preparing graphene oxide |
| WO2015060782A1 (en) * | 2013-10-21 | 2015-04-30 | Hwv Technologies Pte. Ltd. | Graphene oxide/polymer composite membranes and methods of forming thereof |
| CN104556016A (en) * | 2015-01-23 | 2015-04-29 | 青岛科技大学 | Low-temperature environment-friendly preparation method of graphene |
| CN104860302A (en) * | 2015-04-28 | 2015-08-26 | 南京信息工程大学 | Preparation method of wide interlayer spacing and easily-striping graphite oxide |
| CN108069415A (en) * | 2018-01-18 | 2018-05-25 | 燕山大学 | A kind of preparation method of the graphene aerogel of size classification |
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Application publication date: 20190806 |