CN102153077A - Method for preparing single-layer graphene with high carbon-oxygen ratio - Google Patents
Method for preparing single-layer graphene with high carbon-oxygen ratio Download PDFInfo
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Abstract
The invention discloses a method for preparing single-layer graphene with high carbon-oxygen ratio, belonging to the technical field of preparation of functional materials. The method comprises the following steps: taking natural flake graphite as the raw material, preparing graphite oxide by an improved hummers method and carrying out washing with 5% of dilute hydrochloric acid and deionized water until SO4<2-> is eliminated, wherein the mass ratio of flake graphite to potassium permanganate to concentrated nitric acid to concentrated sulfuric acid to hydrogen peroxide is 1:1.5:7.0:10.7:1.5; and taking and expanding the graphite oxide in a muffle furnace at the temperature of 900-1000 DEG C, taking alcohol as a dispersing agent to carry out ultrasonic treatment on the expanded graphite for 1 hour, then carrying out hydrothermal reduction, subjecting the expanded graphite and hydrazine hydrate in a mass ratio of 1:10 to carry out hydrothermal reaction at the temperature of 100 DEG C for 24 hours and washing and drying the product. The method has the following beneficial effects: the single-layer graphene with high carbon-oxygen ratio can be prepared by the method; the yield is high; and the method can be applied to mass production.
Description
Technical field
Have the preparation method of the single-layer graphene of high carbon-to-oxygen ratio but the present invention relates to a kind of mass production simple to operate, belong to the preparing technical field of functional materials.
Technical background
Single-layer graphene is the closelypacked two dimensional crystal structure of monoatomic layer, wherein carbon atom be with six-ring form periodic arrangement in the Graphene plane.This novel two-dimentional carbon material has the performance of many excellences, has caused researchist's extensive concern since 2004 are found.Graphene is to be prevalent in other carbon materials, and can be regarded as the component units of other dimension carbon-based materials: can be regarded as by the Graphene monolithic through piling up and forming as three-dimensional graphite; The soccerballene of zero dimension can be regarded as to be reunited by particular graphite alkene shape and forms; And Graphene just can form the unidimensional carbon nanotube structure after curling.
Although Graphene has only a carbon atom thickness, be the thinnest a kind of in the known materials, yet very firmly hard, it is also stronger than diamond, the best in the world iron and steel of its strength ratio is also high 100 times.Graphene also is the outstanding material of present known conductive performance, and its electronic motion speed has reached 1/300 of the light velocity, considerably beyond the movement velocity of electronics in general conductor.In addition, Graphene also has the performance of many excellences: as higher Young's modulus (1100GPa), thermal conductivity (5000wm
-1K
-1), higher carrier mobility (2 * 10
5Cm
2V
-1S
-1), big specific surface area (calculated value 2630cmg
-1), ferromegnetism etc.Be considered to have wide practical use at aspects such as quantum device, functional composite material, energy storage material, support of the catalyst such as single-molecule detection device, unicircuit, field-effect transistors.The preparation and the utilisation technology of further investigation Graphene, help China's raw material of wood-charcoal material industry restructuring, to high added value, the novel nano-material direction of less energy-consumption develops, more help China's new forms of energy industry, the upgrading of aerospace material, the forward-looking and applicability of the basis of Graphene and performance study has good prospect.
Preparation method commonly used at present comprises: micromechanics is peeled off method, epitaxial growth method and chemical method.Wherein the production cost of chemical method is cheap relatively, and can realize mass production, becomes one of focus of present research.The basic ideas of this method are, under certain condition, peel off in some polarizable medium and disperse graphite and be oxidized to graphene oxide, handle obtaining Graphene again through chemical reduction.
Summary of the invention
The purpose of this invention is to provide a kind of preparation method with single-layer graphene of high carbon-to-oxygen ratio, adopt natural flake graphite, get graphite oxide with improvement hummers legal system, and in retort furnace, carry out high temperature and expand, make expanded graphite, carry out drastic reduction with certain density hydrazine hydrate, had the single-layer graphene of high carbon-to-oxygen ratio in a large number.
A kind of preparation method with single-layer graphene of high carbon-to-oxygen ratio comprises the steps:
(1) preparation of graphite oxide: in the exsiccant reactor, add 98% vitriol oil and 98% concentrated nitric acid, preferred 23: 10 of the volume ratio of 98% vitriol oil and 98% concentrated nitric acid, be cooled to 0 ℃, stir the adding crystalline flake graphite, the mass ratio of concentrated nitric acid and graphite is 7-8: 1, after stirring, slowly add potassium permanganate, the mass ratio of potassium permanganate and graphite is 1.5-2: 1, and control reaction temperature is no more than 15 ℃, stirs 10min.Again reactor is placed 35 ℃ water bath with thermostatic control, evenly stirring reaction 2h.Add deionized water then in the 30min, the mass ratio 1 of graphite and deionized water: 20-30, control reaction temperature is lower than 100 ℃.Add the deionized water termination reaction, add mass concentration 30%H simultaneously
2O
2The aqueous solution, the mass ratio 1 of graphite and aqueous hydrogen peroxide solution: 1.5-2, filtered while hot, and with 5% HCl and deionized water wash to there not being SO
4 2-(use BaCl
2Solution detects), be placed on dry 24h in 60 ℃ the baking oven then.Products therefrom is graphite oxide.
(2) preparation of the single-layer graphene of high carbon-to-oxygen ratio: with graphite oxide 900 ℃ of-1000 ℃ of high temperature expansion 15-30s in retort furnace of step (1), make expanded graphite, add dehydrated alcohol then and disperse every 1g graphite oxide 20ml dehydrated alcohol, and supersound process 1h.The hydrazine hydrate that adds mass concentration 50% then, the mass ratio of expanded graphite and hydrazine hydrate aqueous solution are 1: 8-12, evenly stir back hydro-thermal 24h under 100 ℃ of conditions.After reaction finishes, the sample filtering separating, washing, and in 60 ℃ vacuum drying oven, dry, promptly make single-layer graphene with high carbon-to-oxygen ratio.
The present invention adopts improvement hummers legal system to get the graphite oxide of mild oxidation, at this moment, and SO
4 2-And NO
3 -Form covalent linkage with the carbon of graphite linings, intercalation has destroyed the original Van der Waals force of its interlayer in graphite linings, and its interlamellar spacing is increased.The graphite oxide that is inserted with intercalation compound is when running into high temperature, the a large amount of oxy radical of interlayer will decompose, produce a kind of along the axial thrust of graphite layers C, this motivating force is much larger than graphite oxide interlayer bonding force, under the effect of this motivating force, the graphite oxide interlayer is stripped from, and forms the graphite oxide of the mild oxidation with single layer structure.Under the reductive action of excess hydrazine hydrate, mono-layer graphite oxide is reduced to the single-layer graphene with high carbon-to-oxygen ratio.
Gained Graphene smooth surface illustrates the no big group in Graphene surface, and big oxygen-containing functional group is reduced.Almost not having oxygen-containing functional group in the Graphene, is a kind of Graphene with high carbon-to-oxygen ratio therefore.
Description of drawings
The single-layer graphene with high carbon-to-oxygen ratio of Fig. 1 embodiment 1 preparation and X-ray diffraction (XRD) collection of illustrative plates of graphite oxide, wherein 1 is the single-layer graphene XRD figure with high carbon-to-oxygen ratio of embodiment 1 preparation, 2 is the XRD figure of natural graphite.
Fig. 2 is single-layer graphene scanning electron microscope (SEM) photo with high carbon-to-oxygen ratio of embodiment 1 preparation.
The single-layer graphene with high carbon-to-oxygen ratio of real embodiment 1 preparation of Fig. 3 and the infrared spectra of graphite oxide wherein a are the single-layer graphene infrared spectrogram (IR) with high carbon-to-oxygen ratio of embodiment 1 preparation, and b is the infrared spectrogram (IR) of graphite oxide.
Embodiment
Below in conjunction with the drawings and specific embodiments, further illustrate substantive distinguishing features of the present invention and remarkable advantage, the present invention only is confined to the embodiment that stated by no means.
1). take by weighing the 20g crystalline flake graphite.
2). the crystalline flake graphite that will take by weighing is dissolved in the mixed acid solution of being made up of the concentrated nitric acid of the vitriol oil of 230ml 98% and 100ml 98%, and constantly stirs, and the concentrated nitric acid and the vitriol oil are the commercially available concentrated nitric acid and the vitriol oil.
3). under continuous agitation condition, add potassium permanganate 30g, control reaction temperature is no more than 15 ℃, stirs 10min.Then beaker is placed 35 ℃ water bath with thermostatic control, evenly stirring reaction 2h.Slowly add the 500ml deionized water then, control reaction temperature is lower than 100 ℃.
4) behind the .30min, add 1.2L deionized water termination reaction.Add 30ml 30%H simultaneously
2O
2, filtered while hot, and with 5% HCl and deionized water wash to there not being SO
4 2-(use BaCl
2Solution detects), be placed on dry 24h in 60 ℃ the baking oven then.Products therefrom is graphite oxide.
5). get the 2g graphite oxide, 1000 ℃ of swollen 20s make expanded graphite in retort furnace.
6). in above-mentioned expanded graphite, add the 400ml dehydrated alcohol and disperse, and supersound process 1h.Add 40ml hydrazine hydrate (mass concentration 50%) then, evenly stir back hydro-thermal 24h under 100 ℃ of conditions.After reaction finishes, the sample filtering separating, washing, and in 60 ℃ vacuum drying oven, dry.Promptly make single-layer graphene with high carbon-to-oxygen ratio.
X ray diffracting spectrum by Fig. 1 can be seen, curve 2 expression natural flake graphite laminate structures characteristic peak be 26.61 °, intensity is extremely strong, and the Graphene of the reaction gained of curve 1 expression is very weak 26.61 ° characteristic peak intensity, almost disappear, illustrate that the original laminate structure of graphite is destroyed, form single laminate structure, no diffraction peak occurs.
Also be can be observed by Fig. 2, the Graphene of gained becomes the transparent sheet structure of individual layer.Find out the Graphene smooth surface from figure, the no big group in Graphene surface is described, big oxygen-containing functional group is reduced.
Can draw by Fig. 3 IR spectrogram, curve b is the IR spectrogram of graphite oxide, oxygen-containing functional group in the graphite oxide is after handling through the hydrazine hydrate reduction agent, the infrared spectrum of prepared Graphene (shown in the curve a) is almost straight line, can draw thus and almost not have oxygen-containing functional group, the Graphene that obtains having high carbon-to-oxygen ratio in the Graphene.
Claims (2)
1. the preparation method with single-layer graphene of high carbon-to-oxygen ratio is characterized in that, comprises the steps:
(1) preparation of graphite oxide: in the exsiccant reactor, add 98% vitriol oil and 98% concentrated nitric acid, be cooled to 0 ℃, stir the adding crystalline flake graphite, the mass ratio of concentrated nitric acid and graphite is 7-8: 1, after stirring, slowly add potassium permanganate, the mass ratio of potassium permanganate and graphite is 1.5-2: 1, and control reaction temperature is no more than 15 ℃, stirs 10min, again reactor is placed 35 ℃ water bath with thermostatic control, evenly stirring reaction 2h; Add deionized water then in the 30min, the mass ratio 1 of graphite and deionized water: 20-30, control reaction temperature is lower than 100 ℃, adds the deionized water termination reaction, adds mass concentration 30%H simultaneously
2O
2The aqueous solution, the mass ratio 1 of graphite and aqueous hydrogen peroxide solution: 1.5-2, filtered while hot, and with 5% HCl and deionized water wash to there not being SO
4 2-, being placed on dry 24h in 60 ℃ the baking oven then, products therefrom is graphite oxide;
(2) preparation of the single-layer graphene of high carbon-to-oxygen ratio: with graphite oxide 900 ℃ of-1000 ℃ of high temperature expansion 15-30s in retort furnace of step (1), make expanded graphite, add dehydrated alcohol then and disperse every 1g graphite oxide 20ml dehydrated alcohol, and supersound process 1h; The hydrazine hydrate that adds mass concentration 50% then, the mass ratio of expanded graphite and hydrazine hydrate aqueous solution is 1: 8-12, evenly stir back hydro-thermal 24h under 100 ℃ of conditions, after reaction finishes, the sample filtering separating, washing, and in 60 ℃ vacuum drying oven, dry, promptly make single-layer graphene with high carbon-to-oxygen ratio.
2. according to the method for claim 1, it is characterized in that the volume ratio of the middle vitriol oil of step (1) and concentrated nitric acid 23: 10.
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