CN103241734B - Reduction method of graphene oxide - Google Patents
Reduction method of graphene oxide Download PDFInfo
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- CN103241734B CN103241734B CN201310186059.XA CN201310186059A CN103241734B CN 103241734 B CN103241734 B CN 103241734B CN 201310186059 A CN201310186059 A CN 201310186059A CN 103241734 B CN103241734 B CN 103241734B
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- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
- C01B32/182—Graphene
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- C—CHEMISTRY; METALLURGY
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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 grapheme material preparing technical field; For technical fields such as semi-conductor, solar cell, sensor, nanoelectronics, high-performance nanometer electronic device, matrix material, field emmision material, gas sensor and stored energies.
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 around respectively with 3 the most contiguous carbon atoms, and remaining 1 p electronics, perpendicular to the surface of Graphene, forms π key with atom around.Under finite temperature, Graphene can freely exist, and its thickness only has 0.3354nm, is to find in the world at present the thinnest material (preparation of Graphene, sign and characteristic research progress, Li Xingao, Wang Bolin, Liu Zhongru, material Leader, 2012,26(1): 61-65).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 nanometer circuit.
The preparation method of Graphene mainly contains three major types: (1) peels off graphite method, take graphite as raw material, adopts different synusia lift-off technologies to obtain Graphene, as mechanically peel method, oxidation reduction process, liquid phase stripping method, electrostatic deposition, quench method.(2) direct growth method, 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, by the tube wall of carbon nanotube " incision " vertically, obtains Graphene after flattening, this method productive rate is high, can obtain in batches that size is controlled, the graphene nano band of neat in edge.
It is to generally acknowledge at present cheapness to obtain in a large number the approach of Graphenes that oxidation reduction process is prepared Graphene.First graphite oxidation is formed to graphite oxide, then by ultrasonic dispersion, peel off, obtain graphene oxide, this graphene oxide has lost electroconductibility, and has very strong wetting ability, 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).Conventional reductive agent has hydrazine hydrate, metal hydride, hydroiodic acid HI etc.
In conventional reductive agent, metal hydride is because it is nontoxic, non-corrosiveness, the high and low price of efficiency and be widely used in the reduction of graphene oxide.But be subject to the impact of the reductibility of metal hydride, part oxygen-containing functional group remains in Graphene surface, and reduction reaction is not thorough.The various oxygen-containing functional groups on graphene oxide surface, comprise hydroxyl, carboxyl, epoxy group(ing), carbonyl etc., the carboxyl that metal hydride can reduce wherein efficiently, epoxy group(ing), carbonyl, and almost can not reduce hydroxyl, therefore affected the service efficiency of metal hydride reduction graphene oxide.
Improve the reduction efficiency of metal hydride to graphene oxide, develop a kind of cheapness, nontoxic, free of contamination method of reducing becomes the problem that this area need to solve.
Summary of the invention
For overcoming existing oxidation reduction process, prepare Graphene, the oxygen-containing functional group existing remains in Graphene surface, reduction reaction is not thorough, therefore affect the defects 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 multi-solvents; Described reduction reaction can be carried out at normal temperatures, without heating.Described reduction reaction can efficiently be removed the oxygen-containing functional group in graphene oxide, and the six-membered ring structure of Graphene is restored.Described method nontoxic pollution-free, efficiently cheap, simple and convenient, without complicated conversion unit, therefore the preparation of industrialization for Graphene provides a paths.
Technical solution of the present invention is achieved in that
A method of reducing for graphene oxide, is characterized in take that metal hydride is as reductive agent, and Lewis acid is catalyzer, redox graphene under room temperature; The reduction of graphene oxide is carried out according to following steps:
E) graphene oxide is distributed in solvent according to the ratio of dispersion concentration 0.2～4mg/ml, by magnetic agitation or high shear mixing or ultra-sonic dispersion method dispersion;
F) add Lewis acid to carry out dispersed with stirring, the lewis acidic concentration that adds is at 1mM～30mM;
G) add metal hydride to 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, with clean-out system, cleaning to pH value, 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 bariumchloride.
Described solvent is a kind of in deionized water, methyl alcohol, ethanol, acetone, tetrahydrofuran (THF) and hexanaphthene.
The carbon atom of the Graphene after 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, in the situation that Lewis acid exists, uses metal hydride reduction graphene oxide, and prepares Graphene.The described raw material of preparing Graphene is graphene oxide, conventionally by graphite oxidation, is peeled off and is obtained.
In the method for preparing reduced graphene of the present invention, temperature is not had to particular requirement, normal temperature can reach reduction effect.
The present invention is under the condition by existing at Lewis acid, with metal hydride, graphene oxide is reduced, the method of preparing Graphene, does not therefore have concrete regulation to graphene oxide, and every graphene oxide obtaining through 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, ultrasonic dispersion etc.The present invention does not limit peeling off means, and all methods that can access 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 of Graphene application, and the feature of environmental protection requirement prepared of Graphene.
(2) metal hydride that the present invention uses is cheap, and nontoxic, contaminative is low, adds Lewis acid can effectively improve its reducing power, improves the quality of the Graphene obtaining.
(3) the present invention does not have particular requirement to temperature of reaction, and room temperature can be carried out reduction reaction, can reduce costs, and saves the energy.
(4) method of the present invention can efficiently be removed the oxygen-containing functional group in 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 efficiency is high, without complex apparatus.
Embodiment
Below in conjunction with embodiment, the present invention is described in detail, and described embodiment helps to understand the present invention, should not be considered as concrete restriction of the present invention.
[embodiment 1]
Be distributed in 100ml methanol solvate 100mg graphene oxide is ultrasonic; In the situation that stirring, add aluminum chloride powder, making its concentration in methyl alcohol is 1mM; Add aluminium lithium hydride powder, making its concentration in methyl alcohol is 10mM, at 25 ℃, reacts 30min again; Reaction finishes rear cleaning to neutral.
Performance test:
The carbon atom of Graphene and the mol ratio of Sauerstoffatom that graphene oxide obtains after reduction are 6.02.
Surface resistivity is: 16K Ω/sq.
[embodiment 2]
Be distributed in 100ml tetrahydrofuran solvent 50mg graphene oxide powder is ultrasonic; In the situation that stirring, add aluminum chloride powder, making its concentration in tetrahydrofuran (THF) is 5mM; Under ceaselessly stirring, add SODIUM BOROHYDRIDE POWDER, making its concentration in tetrahydrofuran (THF) is 10mM, in temperature, is to react 30min at 25 ℃; Reaction finishes rear water and cleans to neutral.
Performance test:
The carbon atom of Graphene and the mol ratio of Sauerstoffatom that graphene oxide obtains after reduction are 6.35.
Surface resistivity is: 15.2K Ω/sq.
[embodiment 3]
Be distributed in 100ml water 100mg graphene oxide powder is ultrasonic; In the situation that stirring, add zinc chloride powder, making its concentration in water is 15mM; Under ceaselessly stirring, add SODIUM BOROHYDRIDE POWDER, making its concentration in water is 10mM, in temperature, is to react 30min at 25 ℃; Reaction finishes rear water and cleans to neutral.
Performance test:
The carbon atom of Graphene and the mol ratio of Sauerstoffatom that graphene oxide obtains after reduction are 6.09.
Surface resistivity is: 15.8K Ω/sq.
[embodiment 4]
Be distributed in 100ml water solvent 400mg graphene oxide powder is ultrasonic; In the situation that stirring, add calcium chloride powder, making its concentration in water is 15mM; Under ceaselessly stirring, add hydrogenation to receive powder, making its concentration in water is 10mM, in temperature, is at 25 ℃, to react 12 hours; Reaction finishes rear water and cleans to neutral.
Performance test:
The carbon atom of Graphene and the mol ratio of Sauerstoffatom that graphene oxide obtains after reduction are 6.12.
Surface resistivity is: 15.1K Ω/sq.
[embodiment 5]
Be distributed in 100ml methanol solvate 20mg graphene oxide is ultrasonic; In the situation that stirring, add aluminum chloride powder, making its concentration in methyl alcohol is 1mM; Add aluminium lithium hydride powder, making its concentration in methyl alcohol is 10mM, reacts 4 hours at 25 ℃ again; Reaction finishes rear cleaning to neutral.
Performance test:
The carbon atom of Graphene and the mol ratio of Sauerstoffatom that graphene oxide obtains after reduction are 5.23.
Surface resistivity is: 23.0K Ω/sq.
[embodiment 6]
Be distributed in 100ml water solvent 400mg graphene oxide powder is ultrasonic; In the situation that stirring, add calcium chloride powder, making its concentration in water is 30mM; Under ceaselessly stirring, add hydrogenation to receive powder, making its concentration in water is 200mM, in temperature, is at 25 ℃, to react 12 hours; Reaction finishes rear water and cleans to neutral.
Performance test:
The carbon atom of Graphene and the mol ratio of Sauerstoffatom that graphene oxide obtains after reduction are 6.30.
Surface resistivity is: 15.1K Ω/sq.
[embodiment 7]
Be distributed in 100ml water solvent 100mg graphene oxide powder is ultrasonic; In the situation that stirring, add calcium chloride powder, making its concentration in water is 15mM; Under ceaselessly stirring, add sodium borohydride powder, making its concentration in water is 300mM, in temperature, is at 25 ℃, to react 12 hours; Reaction finishes rear water and cleans to neutral.
Performance test:
The carbon atom of Graphene and the mol ratio of Sauerstoffatom that graphene oxide obtains after reduction are 5.82.
Surface resistivity is: 16.2K Ω/sq.
Claims (5)
1. a method of reducing for graphene oxide, is characterized in that: take metal hydride as reductive agent, Lewis acid is catalyzer, redox graphene under room temperature; The reduction of graphene oxide is carried out according to following steps:
A) graphene oxide is distributed in solvent according to the ratio of dispersion concentration 0.2～4mg/ml, by magnetic agitation or high shear mixing or ultra-sonic dispersion method dispersion;
B) add Lewis acid to carry out dispersed with stirring, the lewis acidic concentration that adds is at 1mM～30mM;
C) add metal hydride to 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, with clean-out system, cleaning to pH value, 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 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 hexanaphthene.
5. the method for reducing of a kind of graphene oxide according to claim 1, is characterized in that: the carbon atom of the Graphene after reduction and the atomic ratio of Sauerstoffatom are greater than 6; The surface resistivity of described Graphene is less than 15K Ω/sq.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103555326B (en) * | 2013-10-17 | 2015-09-23 | 厦门大学 | A kind of preparation method of oxygen-free Graphene fluorescence quantum |
| JP6357539B2 (en) * | 2014-01-17 | 2018-07-11 | カーボン ナノ エンジニアリング システムズ コーポレイション | Repair method for reduced graphene oxide |
| CN104282736B (en) * | 2014-10-30 | 2018-09-11 | 京东方科技集团股份有限公司 | A kind of combination electrode and preparation 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 |
| CN104629603B (en) * | 2015-02-11 | 2017-09-12 | 上海理工大学 | The metal conditioner and corrosion-resistant coating preparation method of graphene-containing |
| CN105129779B (en) * | 2015-07-30 | 2017-06-06 | 复旦大学 | A kind of electrode of super capacitor preparation method of high-performance reduced graphene |
| 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 |
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| CN102452650A (en) * | 2010-10-27 | 2012-05-16 | 清华大学 | Process for preparing graphene by cryochemical method |
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| CN102452650A (en) * | 2010-10-27 | 2012-05-16 | 清华大学 | Process for preparing graphene by cryochemical method |
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