CN106672958A - Preparation method of graphene oxide - Google Patents
Preparation method of graphene oxide Download PDFInfo
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- CN106672958A CN106672958A CN201710033140.2A CN201710033140A CN106672958A CN 106672958 A CN106672958 A CN 106672958A CN 201710033140 A CN201710033140 A CN 201710033140A CN 106672958 A CN106672958 A CN 106672958A
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- graphene oxide
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- dispersion liquid
- oxide according
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/64—Nanometer sized, i.e. from 1-100 nanometer
Abstract
The invention relates to a preparation method of graphene oxide. The preparation method comprises the following steps: adding 20 to 50mg of graphite oxide powder and 20 to 40mg of fluorinated aluminum powder into 10 to 30ml of dispersion liquid in which an amine compound is dissolved to form a mixed system; shaking, washing and centrifuging the mixed system to obtain a graphene oxide solution, wherein the amine compound comprises imidazole, methyl imidazole, alanine, glycine, threonine, dodecylamine, hexanediamine and diaminooctane. The preparation method has the advantages of considerable yield, simple preparation process, excellent properties of an obtained product and the like.
Description
Technical field
The invention belongs to field of nano material preparation, and in particular to a kind of preparation method of graphene oxide.
Background technology
Graphene is a kind of novel charcoal material, it be it is a kind of be the monolayer carbon atom facestock separated from graphite material
Material, this two-dimentional graphite crystal film strength is 100 times of steel.Graphene has the mechanical strength of superelevation, good conduction
The electrical properties of heat conductivility and uniqueness, thus be with a wide range of applications.
Graphene oxide (graphene oxide) is the oxide of Graphene, after oxidized, oxygen-containing functional group thereon
Increase and make property more active compared with Graphene, nature can be improved via the various reactions with oxygen-containing functional group.
The predominantly organic tool stripping method of method, epitaxial growth method, the oxidation-reduction method of graphene oxide/Graphene are prepared at present
And chemical vapour deposition technique.The amount for preparing graphene oxide using mechanical stripping method and epitaxial growth method is relatively low, and uneven thickness
It is even；Oxidation-reduction method is broadly divided into oxidation thermal reduction and oxidation chemistry reduction, and oxidation thermal reduction prepares graphene oxide often
Higher temperature is required, is consumed energy than larger, and chemical reduction method prepares graphene oxide often using chemical reagent such as hydrazines, these
Reagent has certain toxicity, has harm to human body and environment；Graphene oxide is prepared with chemical vapour deposition technique, production is set
Standby requirement is higher.
The content of the invention
In order to solve the above problems, the invention provides a kind of yield is considerable, preparation condition is less demanding, preparation technology is simple
Single, the graphene oxide production technology of products obtained therefrom good properties.
For above-mentioned technical problem, the technical scheme that proposes is the present invention：
A kind of preparation method of graphene oxide, comprises the following steps：
20~50mg graphite oxides powder and 20~40mg aluminium fluoride powder are added to 10~30ml and are dissolved with amine compound
Dispersion liquid forms mixed system；
The mixed system is shaken, washed, is centrifuged and is obtained graphene oxide solution；
Wherein, the amine compound include imidazoles, Methylimidazole., alanine, glycine, threonine, lauryl amine, hexamethylene diamine and
Octamethylenediamine.
Described graphite oxide is to crystalline flake graphite or highly directional pyrolysis stone using Hummers methods or Staudenmaier methods
Ink carries out aoxidizing the graphite oxide that intercalation is obtained.
Further, the preparation process of the dispersion liquid is as follows：
（1）Isopropanol and DMF are mixed, its matched proportion density is：Isopropanol：N, N- dimethyl formyl
Amine is 5：1；
（2）Take step（1）Solution 50ml, add 2g to have electroactive oligomer of phenylamine,
The relative molecular weight of the oligomer of phenylamine is 600-2000；
The oligomer of phenylamine includes any one in aniline trimer, Tetraaniline, aniline pentamer, the aggressiveness of aniline six
Or two or more combinations；
（3）Using weak base or/and weak acid pH value regulator regulating step（2）In the pH value of solution for preparing so as to PH 11~
Between 12；
（4）By step（3）The solution for obtaining carries out ultrasound at least 30min, you can obtain dispersion liquid.
Further, the step（3）Middle weak base or/and weak acid pH value regulator are ammonia, acetic acid and tetramethyl hydrogen-oxygen
Change one or more in ammonium.
Further, the graphene oxide under the conditions of 80~95 DEG C, is shaken in the dispersion liquid.
Further, the concussion time be at least 24h.
Further, the 500~8000rpm of centrifugal rotational speed, is centrifuged 10~30min；After the completion of centrifugation, it is isolated on
Clear liquid is graphene oxide dispersion.
Further, the concussion of the mixed system adopts ultrasonic wave concussion.
Further, the method for described ultrasonic vibration process is：Power 100W, after ultrasonic vibration 4h, stops, after 12h,
Again ultrasonic vibration 4h, then stops 12h, is so recycled to the ultrasonic vibration time and adds and for 24h.
The graphene oxide preparation method that the present invention is provided after heating, is fluorinated by the way that graphite oxide is mixed with aluminium fluoride
Aluminum molecule just can be plugged into prepared aluminium fluoride intercalation thing between aluminum oxide/graphite layer under relatively low reaction temperature to be had again by small molecule
Machine thing part replaces interlayer aluminium fluoride molecule, under heating decomposes Organic substance, and then allows graphite oxide expansion to peel off, so as to make
Obtain graphene oxide；And the oligomer of phenylamine that with the addition of in dispersion liquid can form π-π complex with graphene oxide, i.e.,
Dispersion of the graphene oxide in disperse medium, dispersion stabilization and redispersibility energy can be substantially improved, also without detriment to oxidation
The unique physical of Graphene, chemical property, and it is simple to operate, implement beneficial to scale.
The preparation method that the present invention is provided has the advantage that：
（1）Operating process is simple, easily-controllable, and post processing is simple, graphene oxide suspension, dispersion fissility is good, uniform particle sizes,
The performance for being capable of stable existence and graphene oxide is uninfluenced；
（2）Hazardness to environment and people is little；
（3）It is prepared by proper scaleization；
（4）It is easy to store and transports, the stable resting period is that room temperature condition is lower more than three months；
（5）By the way that the dispersion liquid and graphene oxide are simply mixed in disperse medium, you can graphene oxide is substantially improved
Dispersion, dispersion stabilization and redispersibility energy in disperse medium, the unique physical, chemistry also without detriment to graphene oxide
Performance, and it is simple to operate, implement beneficial to scale.
Specific embodiment
Embodiment 1
A kind of preparation method of graphene oxide, comprises the following steps：
20mg graphite oxides powder and 20mg aluminium fluoride powder are added to into 20ml it are dissolved with the dispersion liquid of amine compound and forms mixed
Zoarium system；Under the conditions of 85 DEG C, ultrasonic vibration 24h is carried out to mixed system, after washing, centrifugal rotational speed be 500rpm, centrifugation
25min；After the completion of centrifugation, isolated supernatant is graphene oxide dispersion；
The method of ultrasonic vibration process is：Power 100W, after ultrasonic vibration 4h, stops, after 12h, then ultrasonic vibration 4h, Ran Houting
Only 12h, being so recycled to the ultrasonic vibration time adds and for 24h.
Wherein, the amine compound include imidazoles, Methylimidazole., alanine, glycine, threonine, lauryl amine, oneself two
Amine and octamethylenediamine.
The thickness of obtained graphene oxide is 1.05nm.
The preparation process of dispersion liquid is as follows：
（1）Isopropanol and DMF are mixed, its matched proportion density is：Isopropanol：N, N- dimethyl formyl
Amine is 5：1；
（2）Take step（1）Solution 50ml, add 2g to have electroactive relative molecular weight oligomeric for the aniline of 600-2000
Thing,
The oligomer of phenylamine includes any one in aniline trimer, Tetraaniline, aniline pentamer, the aggressiveness of aniline six
Or two or more combinations；
（3）Using weak base or/and weak acid pH value regulator regulating step（2）In the pH value of solution for preparing so as to PH is weak 11
Alkali or/and weak acid pH value regulator are one or more in ammonia, acetic acid and Tetramethylammonium hydroxide；
（4）By step（3）The solution for obtaining carries out ultrasonic 30min, you can obtain dispersion liquid.
Embodiment 2
30mg graphite oxides powder and 40mg aluminium fluoride powder are added to into 30ml it are dissolved with the dispersion liquid of amine compound and forms mixed
Zoarium system；Under the conditions of 95 DEG C, ultrasonic vibration 24h is carried out to mixed system, after washing, set centrifugal rotational speed as 5000rpm, from
Heart 10min；After the completion of centrifugation, isolated supernatant is graphene oxide dispersion；
The method of ultrasonic vibration process is：Power 100W, after ultrasonic vibration 4h, stops, after 12h, then ultrasonic vibration 4h, Ran Houting
Only 12h, being so recycled to the ultrasonic vibration time adds and for 24h.
Wherein, the amine compound include imidazoles, Methylimidazole., alanine, glycine, threonine, lauryl amine, oneself two
Amine and octamethylenediamine.
The thickness of obtained graphene oxide is 1.12nm.
The preparation process of dispersion liquid is as follows：
（1）Isopropanol and DMF are mixed, its matched proportion density is：Isopropanol：N, N- dimethyl formyl
Amine is 5：1；
（2）Take step（1）Solution 50ml, add 2g to have electroactive relative molecular weight oligomeric for the aniline of 600-2000
Thing,
The oligomer of phenylamine includes any one in aniline trimer, Tetraaniline, aniline pentamer, the aggressiveness of aniline six
Or two or more combinations；
（3）Using weak base or/and weak acid pH value regulator regulating step（2）In the pH value of solution for preparing so as to PH is 11, weak
Alkali or/and weak acid pH value regulator are one or more in ammonia, acetic acid and Tetramethylammonium hydroxide；
（4）By step（3）The solution for obtaining carries out ultrasonic 40min, you can obtain dispersion liquid.
Embodiment 3
50mg graphite oxides powder and 30mg aluminium fluoride powder are added to into 10ml it are dissolved with the dispersion liquid of amine compound and forms mixed
Zoarium system；Under the conditions of 80 DEG C, ultrasonic vibration 24h is carried out to mixed system, after washing, set centrifugal rotational speed as 8000rpm, from
Heart 30min；After the completion of centrifugation, isolated supernatant is graphene oxide dispersion；
The method of ultrasonic vibration process is：Power 100W, after ultrasonic vibration 4h, stops, after 12h, then ultrasonic vibration 4h, Ran Houting
Only 12h, being so recycled to the ultrasonic vibration time adds and for 24h.
Wherein, the amine compound include imidazoles, Methylimidazole., alanine, glycine, threonine, lauryl amine, oneself two
Amine and octamethylenediamine.
The thickness of obtained graphene oxide is 0.85nm.
The preparation process of dispersion liquid is as follows：
（1）Isopropanol and DMF are mixed, its matched proportion density is：Isopropanol：N, N- dimethyl formyl
Amine is 5：1；
（2）Take step（1）Solution 50ml, add 2g to have electroactive relative molecular weight oligomeric for the aniline of 600-2000
Thing,
The oligomer of phenylamine includes any one in aniline trimer, Tetraaniline, aniline pentamer, the aggressiveness of aniline six
Or two or more combinations；
（3）Using weak base or/and weak acid pH value regulator regulating step（2）In the pH value of solution for preparing so as to PH is 11, weak
Alkali or/and weak acid pH value regulator are one or more in ammonia, acetic acid and Tetramethylammonium hydroxide；
（4）By step（3）The solution for obtaining carries out ultrasonic 70min, you can obtain dispersion liquid.
Ultimate principle, principal character and the advantages of the present invention of the present invention has been shown and described above.The technology of the industry
Personnel it should be appreciated that the present invention is not restricted to the described embodiments, the simply explanation described in above-described embodiment and description this
The principle of invention, without departing from the spirit and scope of the present invention, the present invention also has various changes and modifications, these changes
Change and improvement is both fallen within scope of the claimed invention.The claimed scope of the invention by appending claims and its
Equivalent thereof equivalent thereof.
Claims (8)
1. a kind of preparation method of graphene oxide, it is characterised in that comprise the following steps：
20~50mg graphite oxides powder and 20~40mg aluminium fluoride powder are added to 10~30ml and are dissolved with amine compound
Dispersion liquid forms mixed system；
The mixed system is shaken, washed, is centrifuged and is obtained graphene oxide solution；
Wherein, the amine compound include imidazoles, Methylimidazole., alanine, glycine, threonine, lauryl amine, hexamethylene diamine and
Octamethylenediamine.
2. the preparation method of graphene oxide according to claim 1, it is characterised in that the preparation process of the dispersion liquid
It is as follows：
（1）Isopropanol and DMF are mixed, its matched proportion density is：Isopropanol：N, N- dimethyl formyl
Amine is 5：1；
（2）Take step（1）Solution 50ml, add 2g to have electroactive oligomer of phenylamine,
The relative molecular weight of the oligomer of phenylamine is 600-2000；
The oligomer of phenylamine includes any one in aniline trimer, Tetraaniline, aniline pentamer, the aggressiveness of aniline six
Or two or more combinations；
（3）Using weak base or/and weak acid pH value regulator regulating step（2）In the pH value of solution for preparing so as to PH 11~
Between 12；
（4）By step（3）The solution for obtaining carries out ultrasound at least 30min, you can obtain dispersion liquid.
3. the preparation method of graphene oxide according to claim 2, it is characterised in that the step（3）Middle weak base or/
It it is one or more in ammonia, acetic acid and Tetramethylammonium hydroxide with weak acid pH value regulator.
4. the preparation method of graphene oxide according to claim 1, it is characterised in that the graphene oxide is described
In dispersion liquid, under the conditions of 80~95 DEG C, shaken.
5. the preparation method of graphene oxide according to claim 1, it is characterised in that the concussion time is at least
24h。
6. the preparation method of graphene oxide according to claim 1, it is characterised in that the centrifugal rotational speed 500~
8000rpm, is centrifuged 10~30min；After the completion of centrifugation, isolated supernatant is graphene oxide dispersion.
7. the preparation method of graphene oxide according to claim 1, it is characterised in that the concussion of the mixed system is adopted
Use ultrasonic wave concussion.
8. the preparation method of graphene oxide according to claim 7, it is characterised in that described ultrasonic vibration process
Method is：Power 100W, after ultrasonic vibration 4h, stops, after 12h, then ultrasonic vibration 4h, then stop 12h, so it is recycled to super
The acoustic shock time of swinging adds and for 24h.
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| CN201710033140.2A CN106672958A (en) | 2017-01-18 | 2017-01-18 | Preparation method of graphene oxide |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110183939A (en) * | 2019-06-26 | 2019-08-30 | 陕西科技大学 | A kind of preparation method of graphene/anti-corrosive paint of epoxy resin |
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Application publication date: 20170517 |