CN103241734A - Reduction method of graphene oxide - Google Patents
Reduction method of graphene oxide Download PDFInfo
- Publication number
- CN103241734A CN103241734A CN201310186059XA CN201310186059A CN103241734A CN 103241734 A CN103241734 A CN 103241734A CN 201310186059X A CN201310186059X A CN 201310186059XA CN 201310186059 A CN201310186059 A CN 201310186059A CN 103241734 A CN103241734 A CN 103241734A
- Authority
- CN
- China
- Prior art keywords
- graphene oxide
- graphene
- metal hydride
- concentration
- reduction
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
- C01B32/182—Graphene
- C01B32/184—Preparation
-
- 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
Abstract
The invention discloses a reduction method of graphene oxide. According to the reduction method, with metal hydride as a reducing agent and lewis acid as a catalyst, graphene oxide is reduced at room temperature. The reduction method comprises the following steps: dispersing the graphene oxide in a solvent according to the dispersing concentration of 0.2mg/ml-4mg/ml by virtue of a magnetic stirring, high-shearing mixing or ultrasonic dispersing method; adding lewis acid, stirring and dispersing, wherein the adding concentration of the lewis acid is 1mM-30mM; adding metal hydride and stirring, wherein the dispersing concentration of the metal hydride is 10mM-300mM, and carrying out reduction reaction for 30 minutes to 12 hours at room temperature; filtering and washing by using a cleaning agent until the pH value is neutral, wherein the cleaning agent is pure water, and the metal hydride is one of lithium aluminum hydride, sodium borohydride and sodium hydride. The reduction method of the graphene oxide is efficient, cheap, non-toxic and pollution-free and capable of efficiently removing oxygen-containing functional groups out of graphene oxide, so that a hexatomic ring structure of the graphene oxide is recovered.
Description
Technical field
The present invention relates to a kind of method of reducing of graphene oxide, belong to the grapheme material preparing technical field; Be used for technical fields such as semi-conductor, solar cell, sensor, nanoelectronics, high-performance nanometer electronic device, matrix material, field emmision material, gas sensor and energy storage.
Background technology
Graphene is compound hexagonal lattice, and basic structure is each carbon atom sp
2Orbital hybridization forms 3 covalent linkage, forms 3 σ keys with the most contiguous 3 carbon atoms on every side respectively, and remaining 1 p electronics is perpendicular to the surface of Graphene, forms the π key with on every side atom.Graphene can freely exist under the finite temperature, and its thickness has only 0.3354nm, is to find the thinnest material (preparation of Graphene, sign and characteristic research progress at present in the world, Li Xingao, Wang Bolin, Liu Zhongru, the material Leader, 2012,26(1): 61-65).The Graphene energy gap is almost nil, intrinsic carrier mobility (1.5 * 104cm
2/ (Vs)) and surpass commercial silicon more than 10 times, be expected to replace the ideal material that silicon becomes the nanometer circuit.
Preparation method of graphene mainly contains three major types: (1) peels off the graphite method, is raw material with graphite namely, adopts different synusia lift-off technologies to obtain Graphene, peels off method, electrostatic deposition, quench method as mechanically peel method, oxidation reduction process, liquid phase.(2) direct growth method is by introducing carbon source synthesizing graphite alkene under certain condition, as solvent-thermal method, organic self-assembly method, arc discharge method, crystal epitaxy.(3) carbon nanotube transformation approach with the tube wall of carbon nanotube " incision " vertically, obtains Graphene after the flattening, this method productive rate height can obtain the graphene nano band of controllable size, neat in edge in batches.
It is that generally acknowledge at present can cheap a large amount of approach that obtain Graphenes that oxidation reduction process prepares Graphene.Earlier graphite oxidation is formed graphite oxide, peel off by ultra-sonic dispersion then, obtain graphene oxide, this graphene oxide has lost electroconductibility, and very strong wetting ability is arranged, can be in pure water stable dispersion.After reduction reaction, can obtain Graphene (Highly Conductive Poly (methyl methacrylate) (PMMA)-Reduced Graphene Oxide Composite Prepared by Self-Assembly of PMMA Latex and Graphene Oxide through Electrostatic Interaction.V.H.Pham, T.T.Dang, S.H.Hur, E.J.Kim and J.S.Chung, ACS Appl.Mater, 2012,4 (5): 2630 – 1638).Reductive agent commonly used has hydrazine hydrate, metal hydride, hydroiodic acid HI etc.
In reductive agent commonly used, metal hydride is because it is nontoxic, non-corrosiveness, efficient height and low price and be widely used in the reduction of graphene oxide.But be subjected to the influence of the reductibility of metal hydride, the part oxygen-containing functional group remains in the Graphene surface, and reduction reaction is not thorough.The various oxygen-containing functional groups on graphene oxide surface comprise hydroxyl, carboxyl, epoxy group(ing), carbonyls etc., metal hydride can reduce carboxyl wherein efficiently, epoxy group(ing), carbonyl, and almost can not reduce hydroxyl, therefore influenced the service efficiency of metal hydride reduction graphene oxide.
Improve metal hydride to the reduction efficiency of graphene oxide, develop a kind of cheapness, nontoxic, free of contamination method of reducing becomes the problem that this area need solve.
Summary of the invention
Prepare Graphene for overcoming existing oxidation reduction process, the oxygen-containing functional group that exists remains in the Graphene surface, reduction reaction is not thorough, therefore influence defectives such as graphene oxide service efficiency, the invention discloses a kind of method of reducing of graphene oxide, described method of reducing adopts cheap, nontoxic, free of contamination metal hydride salt as reductive agent, and in addition a certain proportion of catalyzer improves its reducing power.Described reduction reaction can be carried out in multiple solvent; Described reduction reaction can be carried out at normal temperatures, need not heating.Described reduction reaction can efficiently be removed the oxygen-containing functional group in the graphene oxide, and the six-membered ring structure of Graphene is restored.Described method nontoxic pollution-free, efficient cheap, simple and convenient, need not complicated conversion unit, therefore the preparation of industrialization for Graphene provides a paths.
Technical solution of the present invention is achieved in that
A kind of method of reducing of graphene oxide is characterized in the metal hydride being reductive agent, and Lewis acid is catalyzer, redox graphene under the room temperature; The reduction of graphene oxide is carried out according to following steps:
E) graphene oxide is distributed in the solvent according to the ratio of disperseing concentration 0.2～4mg/ml, by magnetic agitation or high shear mixing or ultra-sonic dispersion method dispersion;
F) add Lewis acid and carry out dispersed with stirring, lewis acidic adding concentration is at 1mM～30mM;
G) add metal hydride and stir, the dispersion concentration of described metal hydride is 10mM～300mM, and reduction reaction is at room temperature carried out 30min～12h;
H) it is neutral filtering, cleaning to the pH value with clean-out system, and described clean-out system is pure water.
Described metal hydride is a kind of during aluminium lithium hydride, sodium borohydride, hydrogenation are received.
Described Lewis acid is a kind of in aluminum chloride, iron(ic) chloride, magnesium chloride, strontium chloride, Cerium II Chloride, calcium chloride and the bariumchloride.
Described solvent is a kind of in deionized water, methyl alcohol, ethanol, acetone, tetrahydrofuran (THF) and the hexanaphthene.
The carbon atom of the Graphene after the reduction and the atomic ratio of Sauerstoffatom are greater than 6; The surface resistivity of described Graphene is less than 15K Ω/sq.
The method of redox graphene of the present invention under the situation that Lewis acid exists, is used the metal hydride reduction graphene oxide, and the preparation Graphene.The raw material of described preparation Graphene is graphene oxide, is peeled off and is got by graphite oxidation usually.
Of the present invention prepare to reduce temperature is not had particular requirement in the method for Graphene, normal temperature can reach reduction effect.
The present invention is by under the condition that exists at Lewis acid, with metal hydride graphene oxide is reduced, therefore the method for preparing Graphene does not have concrete regulation to graphene oxide, and every graphene oxide that obtains through the peroxidation intercalation all goes for the present invention.
The stripping means of graphene oxide of the present invention is the known method of the staff of this area, for example: thermal expansion, microwave expansion, ultra-sonic dispersion etc.The present invention does not do restriction to peeling off means, and all can access the method for graphene oxide, all can be used for the present invention.
Compared with prior art, the present invention has following beneficial effect:
(1) the present invention does not have particular requirement to solvent, and spendable solvent species is more, can adapt to the diversity requirement that Graphene is used, and the feature of environmental protection requirement of Graphene preparation.
(2) the metal hydride cheapness of the present invention's use, nontoxic, contaminative is low, adds Lewis acid and can effectively improve its reducing power, improves the quality of the Graphene that obtains.
(3) the present invention does not have particular requirement to temperature of reaction, and room temperature can be carried out reduction reaction, can reduce cost, and saves the energy.
(4) method of the present invention can efficiently be removed the oxygen-containing functional group in the graphene oxide, and the six-membered ring structure of Graphene is restored; Obtain having the ratio of higher carbon atom and Sauerstoffatom, and the Graphene of lower surface resistivity.
(5) the method for the invention is simple to operate, and the efficient height need not complex apparatus.
Embodiment
The present invention is described in detail below in conjunction with embodiment, and described embodiment helps to understand the present invention, should not be considered as concrete restriction of the present invention.
[embodiment 1]
With 100mg graphene oxide ultra-sonic dispersion in the 100ml methanol solvate; Add aluminum chloride powder under condition of stirring, making its concentration in methyl alcohol is 1mM; Add the aluminium lithium hydride powder again, making its concentration in methyl alcohol is 10mM, reacts 30min down at 25 ℃; Reaction finishes the back and cleans to neutral.
Performance test:
The carbon atom of the Graphene that obtains after the reduction of graphene oxide process and the mol ratio of Sauerstoffatom are 6.02.
Surface resistivity is: 16K Ω/sq.
[embodiment 2]
With 50mg graphene oxide powder ultra-sonic dispersion in the 100ml tetrahydrofuran solvent; Add aluminum chloride powder under condition of stirring, making its concentration in tetrahydrofuran (THF) is 5mM; Add SODIUM BOROHYDRIDE POWDER under ceaselessly stirring, making its concentration in tetrahydrofuran (THF) is 10mM, is 25 ℃ of reaction 30min down in temperature; Reaction finishes the back water and cleans to neutral.
Performance test:
The carbon atom of the Graphene that obtains after the reduction of graphene oxide process and the mol ratio of Sauerstoffatom are 6.35.
Surface resistivity is: 15.2K Ω/sq.
[embodiment 3]
With 100mg graphene oxide powder ultra-sonic dispersion in 100ml water; Add the zinc chloride powder under condition of stirring, making its concentration in water is 15mM; Add SODIUM BOROHYDRIDE POWDER under ceaselessly stirring, making its concentration in water is 10mM, is 25 ℃ of reaction 30min down in temperature; Reaction finishes the back water and cleans to neutral.
Performance test:
The carbon atom of the Graphene that obtains after the reduction of graphene oxide process and the mol ratio of Sauerstoffatom are 6.09.
Surface resistivity is: 15.8K Ω/sq.
[embodiment 4]
With 400mg graphene oxide powder ultra-sonic dispersion in the 100ml water solvent; Add the calcium chloride powder under condition of stirring, making its concentration in water is 15mM; Add hydrogenation and receive powder under ceaselessly stirring, making its concentration in water is 10mM, is 25 ℃ of reactions 12 hours down in temperature; Reaction finishes the back water and cleans to neutral.
Performance test:
The carbon atom of the Graphene that obtains after the reduction of graphene oxide process and the mol ratio of Sauerstoffatom are 6.12.
Surface resistivity is: 15.1K Ω/sq.
[embodiment 5]
With 20mg graphene oxide ultra-sonic dispersion in the 100ml methanol solvate; Add aluminum chloride powder under condition of stirring, making its concentration in methyl alcohol is 1mM; Add the aluminium lithium hydride powder again, making its concentration in methyl alcohol is 10mM, reacts 4 hours down at 25 ℃; Reaction finishes the back and cleans to neutral.
Performance test:
The carbon atom of the Graphene that obtains after the reduction of graphene oxide process and the mol ratio of Sauerstoffatom are 5.23.
Surface resistivity is: 23.0K Ω/sq.
[embodiment 6]
With 400mg graphene oxide powder ultra-sonic dispersion in the 100ml water solvent; Add the calcium chloride powder under condition of stirring, making its concentration in water is 30mM; Add hydrogenation and receive powder under ceaselessly stirring, making its concentration in water is 200mM, is 25 ℃ of reactions 12 hours down in temperature; Reaction finishes the back water and cleans to neutral.
Performance test:
The carbon atom of the Graphene that obtains after the reduction of graphene oxide process and the mol ratio of Sauerstoffatom are 6.30.
Surface resistivity is: 15.1K Ω/sq.
[embodiment 7]
With 100mg graphene oxide powder ultra-sonic dispersion in the 100ml water solvent; Add the calcium chloride powder under condition of stirring, making its concentration in water is 15mM; Add the sodium borohydride powder under ceaselessly stirring, making its concentration in water is 300mM, is 25 ℃ in temperature and reacts 12 hours down; Reaction finishes the back water and cleans to neutral.
Performance test:
The carbon atom of the Graphene that obtains after the reduction of graphene oxide process and the mol ratio of Sauerstoffatom are 5.82.
Surface resistivity is: 16.2K Ω/sq.
Claims (5)
1. the method for reducing of a graphene oxide, it is characterized in that: be reductive agent with the metal hydride, Lewis acid is catalyzer, redox graphene under the room temperature; The reduction of graphene oxide is carried out according to following steps:
A) graphene oxide is distributed in the solvent according to the ratio of disperseing concentration 0.2～4mg/ml, by magnetic agitation or high shear mixing or ultra-sonic dispersion method dispersion;
B) add Lewis acid and carry out dispersed with stirring, lewis acidic adding concentration is at 1mM～30mM;
C) add metal hydride and stir, the dispersion concentration of described metal hydride is 5mM～300Mm, and reduction reaction is at room temperature carried out 30min～12h;
D) it is neutral filtering, cleaning to the pH value with clean-out system, and described clean-out system is pure water.
2. the method for reducing of a kind of graphene oxide according to claim 1 is characterized in that: described metal hydride is a kind of during aluminium lithium hydride, sodium borohydride, hydrogenation are received.
3. the method for reducing of a kind of graphene oxide according to claim 1 is characterized in that: described Lewis acid is a kind of in aluminum chloride, iron(ic) chloride, magnesium chloride, strontium chloride, Cerium II Chloride, calcium chloride and the bariumchloride.
4. the method for reducing of a kind of graphene oxide according to claim 1 is characterized in that: described solvent is a kind of in deionized water, methyl alcohol, ethanol, acetone, tetrahydrofuran (THF) and the hexanaphthene.
5. the method for reducing of a kind of graphene oxide according to claim 1, it is characterized in that: the carbon atom of the Graphene after the reduction and the atomic ratio of Sauerstoffatom are greater than 6; The surface resistivity of described Graphene is less than 15K Ω/sq.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310186059.XA CN103241734B (en) | 2013-05-17 | 2013-05-17 | Reduction method of graphene oxide |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310186059.XA CN103241734B (en) | 2013-05-17 | 2013-05-17 | Reduction method of graphene oxide |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103241734A true CN103241734A (en) | 2013-08-14 |
| CN103241734B CN103241734B (en) | 2014-11-26 |
Family
ID=48921648
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310186059.XA Expired - Fee Related CN103241734B (en) | 2013-05-17 | 2013-05-17 | Reduction method of graphene oxide |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103241734B (en) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103555326A (en) * | 2013-10-17 | 2014-02-05 | 厦门大学 | Preparation method of oxygen-free graphene fluorescence quantum dots |
| CN104282736A (en) * | 2014-10-30 | 2015-01-14 | 京东方科技集团股份有限公司 | Combined electrode, manufacturing method thereof, array substrate and display device |
| CN104617300A (en) * | 2015-02-09 | 2015-05-13 | 天津师范大学 | Method for preparing lithium ion battery anode/cathode material from reduced graphene oxide |
| CN104629603A (en) * | 2015-02-11 | 2015-05-20 | 上海理工大学 | Graphene-containing metal surface treatment agent and preparation method of anti-corrosion coating |
| CN105129779A (en) * | 2015-07-30 | 2015-12-09 | 复旦大学 | Preparation method of high performance reduced graphene for producing electrode of super capacitor |
| EP3085666A4 (en) * | 2014-01-17 | 2017-03-01 | Shenzhen Cantonnet Energy Services Co. , Ltd. | Method for repairing reduced graphene oxide |
| CN109825346A (en) * | 2019-03-04 | 2019-05-31 | 宁波辉宏新材料有限公司 | A kind of compound release agent of graphene and preparation method thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102452650A (en) * | 2010-10-27 | 2012-05-16 | 清华大学 | Process for preparing graphene by cryochemical method |
-
2013
- 2013-05-17 CN CN201310186059.XA patent/CN103241734B/en not_active Expired - Fee Related
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102452650A (en) * | 2010-10-27 | 2012-05-16 | 清华大学 | Process for preparing graphene by cryochemical method |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103555326A (en) * | 2013-10-17 | 2014-02-05 | 厦门大学 | Preparation method of oxygen-free graphene fluorescence quantum dots |
| CN103555326B (en) * | 2013-10-17 | 2015-09-23 | 厦门大学 | A kind of preparation method of oxygen-free Graphene fluorescence quantum |
| EP3085666A4 (en) * | 2014-01-17 | 2017-03-01 | Shenzhen Cantonnet Energy Services Co. , Ltd. | Method for repairing reduced graphene oxide |
| CN104282736A (en) * | 2014-10-30 | 2015-01-14 | 京东方科技集团股份有限公司 | Combined electrode, manufacturing method thereof, array substrate and display device |
| CN104617300A (en) * | 2015-02-09 | 2015-05-13 | 天津师范大学 | Method for preparing lithium ion battery anode/cathode material from reduced graphene oxide |
| CN104629603A (en) * | 2015-02-11 | 2015-05-20 | 上海理工大学 | Graphene-containing metal surface treatment agent and preparation method of anti-corrosion coating |
| CN105129779A (en) * | 2015-07-30 | 2015-12-09 | 复旦大学 | Preparation method of high performance reduced graphene for producing electrode of super capacitor |
| CN109825346A (en) * | 2019-03-04 | 2019-05-31 | 宁波辉宏新材料有限公司 | A kind of compound release agent of graphene and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103241734B (en) | 2014-11-26 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103241734B (en) | Reduction method of graphene oxide | |
| CN107362801B (en) | Hydrotalcite-based single-atomic-layer cobalt/cobalt oxide composite-structure electrocatalyst and preparation method and application thereof | |
| CN105776154A (en) | Preparation method of tungsten diselenide nanosheet | |
| CN102225757B (en) | Graphdiyne nanofilm and preparation method thereof | |
| Wada et al. | Fabrication of bismuth telluride nanoplates via solvothermal synthesis using different alkalis and nanoplate thin films by printing method | |
| CN102452650B (en) | Process for preparing graphene by cryochemical method | |
| CN103420365B (en) | A kind of method preparing Graphene | |
| CN108358191B (en) | Low-defect graphene and preparation method thereof | |
| CN103382026A (en) | Low-cost mass preparation method of high-quality graphene | |
| CN102530926A (en) | Method for preparing graphene based on hydrosulfite | |
| Wei et al. | Preparation of Cu2O nanorods by a simple solvothermal method | |
| CN104445160B (en) | Method for preparing graphene through molten inorganic salt reaction bed | |
| CN103408000A (en) | Preparation method for oxidized grapheme in large sheet | |
| CN104556017B (en) | A kind of magnanimity preparation method of high-quality graphene | |
| CN102320597B (en) | Preparation method of graphene | |
| CN103864137B (en) | Flower shape zinc oxide nano material and preparation method thereof | |
| CN103626163A (en) | Graphene preparation method | |
| CN103570007A (en) | Preparation method of graphite oxide | |
| CN103601177B (en) | Method for preparing graphene from solid organic acid by using alkali metal salt as catalyst | |
| CN107416811A (en) | A kind of preparation method of high conductivity graphene | |
| CN105754414B (en) | A kind of conducting nano copper ink and preparation method thereof | |
| CN102205959A (en) | Graphite alkene nanotube and preparation method thereof | |
| CN104058399A (en) | Direct preparation method of high-purity high-quality graphene | |
| WO2016070396A1 (en) | Method for preparing graphene by molten state inorganic salt reaction bed | |
| CN104108712B (en) | A kind of boron doped graphene and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20141126 Termination date: 20170517 |