CN109052385A - A kind of preparation method of graphene oxide - Google Patents
A kind of preparation method of graphene oxide Download PDFInfo
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- CN109052385A CN109052385A CN201811132372.4A CN201811132372A CN109052385A CN 109052385 A CN109052385 A CN 109052385A CN 201811132372 A CN201811132372 A CN 201811132372A CN 109052385 A CN109052385 A CN 109052385A
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- graphene oxide
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- C01—INORGANIC CHEMISTRY
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- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
- C01B32/182—Graphene
- C01B32/198—Graphene oxide
Abstract
The present invention discloses a kind of preparation method of graphene oxide, wherein, the method includes insertions after connecting to power supply graphite anode and stainless steel cathode respectively equipped in the electrolytic cell of electrolyte, the electrolyte is made of principal component, additive and deionized water, and the principal component is one or both of sodium carbonate and sodium phosphate；Power on, the electrolyte generates liquid phase plasma in the energized state and carries out arc discharge, and the graphite is quickly removed and aoxidized in the arc discharge that the liquid phase plasma generates, and graphene oxide is made.The arc voltage that the present invention is generated by liquid phase plasma can quickly remove and graphite oxide, to effectively improve graphene oxide production efficiency, and method flow of the invention is simple, easily operated, yield is high, does not use strong oxidizer, it is environmental-friendly, it is suitable for industrialization large-scale production.
Description
Technical field
The present invention relates to graphene oxide field more particularly to a kind of preparation methods of graphene oxide.
Background technique
Graphene (graphene) is that a kind of atomic thickness, the two dimension for the honeycomb structure being made of sp2 carbon atom are thin
Piece, graphene oxide (graphene oxide, GO) are the graphene of oxidation, contain C-O key and/or C=O key, wherein C-O
Carbon is sp3 hydridization in key, and carbon is sp2 hydridization in C=O key.Graphene oxide still prepares stone other than with excellent performance
The important source material of black alkene, in recent years by extensive concern.
The main preparation methods of graphene oxide are the method for Hummers et al. exploitation, use potassium permanganate in concentrated sulfuric acid
It is then ultrasonic in the solution with sodium nitrate graphite oxide, obtain graphene oxide.Although this method high-volume work easy to accomplish
Industry production, but the reaction time is long, generally requires reaction a couple of days, and there are high concentrated acid and oxidant, harmful by-products and
The processing of waste water has aggravated the burden of environment.
Electrochemical method can remove/and oxidation prepares graphene or graphene oxide, abandon the strong acid and oxygen of high concentration
Agent has preferable market prospects.Such as the patent that University of Manchester submits (application number: 201480072668.5) uses
Organic anion, non-oxidizable polyatomic anion, polyatomic anion etc. are the main component of electrolyte, by electrochemistry side
Method removing/graphite oxide becomes graphene oxide, but due to using Conventional electrochemical method, so the life of graphene oxide
Production efficiency is lower, and the reaction time is still longer.
Therefore, the existing technology needs to be improved and developed.
Summary of the invention
In view of above-mentioned deficiencies of the prior art, the purpose of the present invention is to provide a kind of preparation method of graphene oxide,
Aim to solve the problem that the problem that the production technology of existing graphene oxide is complicated and production efficiency is low.
Technical scheme is as follows:
A kind of preparation method of graphene oxide, wherein comprising steps of
Using graphite as anode, stainless steel is as cathode, and insertion is equipped with electricity after the anode and cathode is connected to power supply respectively
In the electrolytic cell for solving liquid, the electrolyte is made of principal component, additive and deionized water, and the principal component is sodium carbonate and phosphorus
One or both of sour sodium；
Power on, the electrolyte generates liquid phase plasma in the energized state and carries out arc discharge, the liquid phase etc.
The graphite is quickly removed and is aoxidized in the arc discharge that gas ions generate, and graphene oxide is made.
The preparation method of the graphene oxide, wherein the concentration of the principal component is 5-50g/L.
The preparation method of the graphene oxide, wherein the additive is glycerol, neopelex, second
One of two pure and mild sodium tetraborates are a variety of.
The preparation method of the graphene oxide, wherein the concentration of the additive is 0.5-2g/L.
The preparation method of the graphene oxide, wherein the pH value of the electrolyte is 8-14.
The preparation method of the graphene oxide, wherein the power supply is direct current pulse power source or AC power source.
The preparation method of the graphene oxide, wherein the voltage after the power supply is connected is 50-2000V and/or electricity
Stream is 1-2000mA/cm2。
The preparation method of the graphene oxide, wherein the bottom of the electrolytic cell is provided with several ultrasonic vibrators.
The preparation method of the graphene oxide, wherein the power of the ultrasonic vibrator is 300-900W.
The preparation method of the graphene oxide, wherein be additionally provided in the electrolytic cell for controlling electrolyte temperature
The heat exchanger of degree.
The utility model has the advantages that the preparation method of graphene oxide provided by the invention is different from traditional electrochemical method, at this
In invention, after power supply is connected, make electrolyte ionization that there is aura or arc to generate in electrode zone by applying high pressure
The liquid phase plasma of light, the arc voltage that the liquid phase plasma generates can quickly remove and graphite oxide, to make
Obtain graphene oxide；Further, the present invention also assists promoting the removing and dispersion of graphite by ultrasonic wave, and the present invention significantly mentions
The high production efficiency of graphene oxide, is reduced to a few houres for several days outputs of conventional method, even in dozens of minutes
It can be completed, and the present invention does not use strong oxidizer, it is environmental-friendly.
Detailed description of the invention
Fig. 1 is the electrolytic cell device schematic diagram that the present invention is used to prepare graphene oxide, wherein 1 is electrolytic cell, and 2 be heat
Exchanger, 3 be anode, and 4 be cathode, and 5 be electrolyte, and 6 be ultrasonic vibrator, and 7 be power supply, and 8 be the liquid phase plasma generated.
Fig. 2 is the scanning electron microscope (SEM) photograph of graphene oxide prepared by the present invention.
Fig. 3 is the Raman map of graphene oxide prepared by the present invention.
Specific embodiment
The present invention provides a kind of preparation methods of graphene oxide, to make the purpose of the present invention, technical solution and effect
Clearer, clear, the present invention is described in more detail below.It should be appreciated that specific embodiment described herein is only used
To explain the present invention, it is not intended to limit the present invention.
Referring to Fig. 1, Fig. 1 is the electrolytic cell device schematic diagram that the present invention is used to prepare graphene oxide, as shown, this
Invention is during preparing graphene oxide, and using graphite as anode, stainless steel is as cathode, by the anode and cathode point
Insertion is equipped in the electrolytic cell of electrolyte after not connecting to power supply, and the electrolyte is by principal component, additive and deionized water group
At the principal component is one or both of sodium carbonate and sodium phosphate；
Power on, the electrolyte generates liquid phase plasma in the energized state and carries out arc discharge, the liquid phase etc.
The graphite is quickly removed and is aoxidized in the arc discharge that gas ions generate, and graphene oxide is made.
Specifically, the present invention mainly passes through application voltage and ionizes to the principal component in electrolyte, thus in electrode
Region generates the liquid phase plasma with arc light, and the liquid phase plasma then passes through arc discharge and shells to anode graphite
From oxidation, so that graphene oxide quickly be made.
Further, in the present invention, the concentration of the principal component is preferably 5-50g/L.It is generated when the concentration of principal component
One key factor of liquid phase plasma, only when the concentration of principal component be greater than 5g/L, could ionize after powered up generation tool
There is the liquid phase plasma of arc light, with the increase of concentration, the arc voltage that the liquid phase plasma generates also is gradually increased.
When the concentration of principal component is greater than 50g/L, then the arc voltage that the liquid phase plasma generates is excessive, is difficult to control oxidation stone
The generation of black alkene.
Further, the additive in electrolyte of the present invention is the auxiliary element for exciting liquid phase plasma, has limit
System and stable plasma and the function of promoting graphite removing and dissolution, as a wherein specific embodiment, the additive
Preferably one of glycerol, neopelex, ethylene glycol and sodium tetraborate or a variety of.
Preferably, the concentration of the additive is 0.5-2g/L, and in the concentration range, the additive can effectively promote
It removes and dissolves into graphite.
Further, the present invention adjusts the pH value of electrolyte, the pH of the preferably described electrolyte by addition sodium hydroxide
Value is 8-14, and in the range, the power supply can apply higher voltage to ionize electrolyte and generate liquid phase plasma.
Preferably, the voltage after the power supply is connected is 50-2000V and/or electric current is 1-2000mA/cm2.As act
Example, the voltage can be 500V, 800V, 1500V, 2000V etc.；The electric current is 200 mA/cm2、500 mA/cm2、1000
mA/cm2、1500 mA/cm2Deng.
It is further preferred that the power supply is direct current pulse power source or AC power source.Specifically, when the power supply is straight
Flow the pulse power or when AC power source, the arc voltage of the liquid phase plasma be it is intermittent, when generating arc voltage
When, the temperature of electrolyte can increase, and when not generating arc voltage, the temperature of the electrolyte can then be reduced, and pass through
The mode of the high/low temperature cataclysm can accelerating anode graphite removing, to promote the production efficiency of graphene oxide.
Preferably, the present invention is also provided with the heat exchanger for controlling electrolyte temperature in a cell, the heat is handed over
Parallel operation keeps desired value for controlling electrolyte temperature, and temperature is too low can not to generate arc discharge；The too high arc discharge of temperature is not
It is enough to stablize, it is unable to steady production.
Further, in the present invention, the bottom of the electrolytic cell is provided with several ultrasonic vibrators, when power supply is connected
Afterwards, the ultrasonic vibrator starts simultaneously and anode graphite is removed and dispersed, it is preferable that the power of the ultrasonic vibrator is
300-900W, in the range, power are bigger, and peeling effect is better.
Explanation is further explained to a kind of preparation method of graphene oxide of the present invention below by specific embodiment:
Embodiment 1
Electrolyte principal component be 5g/L sodium carbonate, additive be 0.5g/L glycerol, and using sodium hydroxide adjust pH value to
8, electrolyte temperature is 20 degrees Celsius；Use direct current pulse power source, voltage 50V, current density 2000mA/cm2。
Reaction time is 1 hour, and the graphene oxide number of plies is 1-10 layers, yield 51%, the scanning electron microscope of test such as Fig. 2
Shown, Raman map is as shown in Figure 3, it is seen that generates graphene oxide.
Embodiment 2
Electrolyte principal component is the sodium phosphate of 10g/L and the sodium citrate of 20g/L, and additive is the detergent alkylate sulphur of 0.5g/L
The ethylene glycol of sour sodium and 2g/L, and pH value is adjusted to 14 using sodium hydroxide, electrolyte temperature is 60 degrees Celsius；Use direct current arteries and veins
Rush power supply, voltage 2000V, current density 2000mA/cm2。
Reaction time is 15 minutes, and the graphene oxide number of plies is 1-10 layers, yield 75%.
Embodiment 3
Electrolyte principal component is the sodium phosphate of the sodium carbonate of 50g/L, 20g/L, and additive is the neopelex of 2g/L
With the sodium tetraborate of 0.5g/L, and pH value is adjusted to 10 using sodium hydroxide, electrolyte temperature is 40 degrees Celsius；Use alternating current
Source, voltage 400V, current density 1mA/cm2。
Reaction time is 12 hours, and the graphene oxide number of plies is 1-10 layers, yield 81%.
In conclusion the preparation method of graphene oxide provided by the invention is different from traditional electrochemical method, at this
In invention, after power supply is connected, make electrolyte ionization that there is aura or arc to generate in electrode zone by applying high pressure
The liquid phase plasma of light, the arc voltage that the liquid phase plasma generates can quickly remove and graphite oxide, to make
Obtain graphene oxide；Further, the present invention also assists promoting the removing and dispersion of graphite by ultrasonic wave.The present invention significantly mentions
The high production efficiency of graphene oxide, is reduced to a few houres for several days outputs of conventional method, even in dozens of minutes
It can be completed.
It should be understood that the application of the present invention is not limited to the above for those of ordinary skills can
With improvement or transformation based on the above description, all these modifications and variations all should belong to the guarantor of appended claims of the present invention
Protect range.
Claims (10)
1. a kind of preparation method of graphene oxide, which is characterized in that comprising steps of
Using graphite as anode, stainless steel is as cathode, and insertion is equipped with electricity after the anode and cathode is connected to power supply respectively
In the electrolytic cell for solving liquid, the electrolyte is made of principal component, additive and deionized water, and the principal component is sodium carbonate and phosphorus
One or both of sour sodium；
Power on, the electrolyte generates liquid phase plasma in the energized state and carries out arc discharge, the liquid phase etc.
The graphite is quickly removed and is aoxidized in the arc discharge that gas ions generate, and graphene oxide is made.
2. the preparation method of graphene oxide according to claim 1, which is characterized in that the concentration of the principal component is 5-
50g/L。
3. the preparation method of graphene oxide according to claim 1, which is characterized in that the additive is glycerol, ten
One of dialkyl benzene sulfonic acids sodium, ethylene glycol and sodium tetraborate are a variety of.
4. the preparation method of graphene oxide according to claim 1, which is characterized in that the concentration of the additive is
0.5-2g/L。
5. the preparation method of graphene oxide according to claim 1, which is characterized in that the pH value of the electrolyte is 8-
14。
6. the preparation method of graphene oxide according to claim 1, which is characterized in that the power supply is DC pulse
Source or AC power source.
7. the preparation method of graphene oxide according to claim 1, which is characterized in that the voltage after the power supply connection
It is 1-2000mA/cm for 50-2000V and/or electric current2。
8. the preparation method of graphene oxide according to claim 1, which is characterized in that the bottom of the electrolytic cell is arranged
There are several ultrasonic vibrators.
9. the preparation method of graphene oxide according to claim 8, which is characterized in that the power of the ultrasonic vibrator is
300-900W。
10. the preparation method of graphene oxide according to claim 1, which is characterized in that also set up in the electrolytic cell
There is the heat exchanger for controlling electrolyte temperature.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN113026043A (en) * | 2021-03-02 | 2021-06-25 | 常熟理工学院 | Electrolysis equipment and application thereof |
| CN114450251A (en) * | 2019-06-07 | 2022-05-06 | 德米特里.梅德韦杰夫 | System and method for producing nanocarbon materials by pulsed discharge in liquid |
| CN114774129A (en) * | 2022-03-29 | 2022-07-22 | 中冶南方都市环保工程技术股份有限公司 | Electrolyte for electrically repairing hexavalent chromium polluted soil and electric repairing method |
| CN115010122A (en) * | 2022-06-17 | 2022-09-06 | 中钢集团南京新材料研究院有限公司 | Preparation device, preparation method and application of high-oxidation graphene |
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| CN106629689A (en) * | 2016-12-16 | 2017-05-10 | 复旦大学 | High-efficiency catalysis macroscopic quantity preparation method for graphene oxide or compound thereof reduced and peeled based on microwaves |
| CN107117602A (en) * | 2017-06-15 | 2017-09-01 | 成都新柯力化工科技有限公司 | A kind of method that continuous stripping of arc plasma prepares graphene |
| CN107459031A (en) * | 2016-05-25 | 2017-12-12 | 南京理工大学 | A kind of liquid phase plasma body method for preparing graphene |
| CN107777674A (en) * | 2017-09-26 | 2018-03-09 | 深圳先进技术研究院 | A kind of method that two-dimensional material is prepared using atmospheric plasma |
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| CN107459031A (en) * | 2016-05-25 | 2017-12-12 | 南京理工大学 | A kind of liquid phase plasma body method for preparing graphene |
| CN106629689A (en) * | 2016-12-16 | 2017-05-10 | 复旦大学 | High-efficiency catalysis macroscopic quantity preparation method for graphene oxide or compound thereof reduced and peeled based on microwaves |
| CN107117602A (en) * | 2017-06-15 | 2017-09-01 | 成都新柯力化工科技有限公司 | A kind of method that continuous stripping of arc plasma prepares graphene |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN114450251A (en) * | 2019-06-07 | 2022-05-06 | 德米特里.梅德韦杰夫 | System and method for producing nanocarbon materials by pulsed discharge in liquid |
| CN113026043A (en) * | 2021-03-02 | 2021-06-25 | 常熟理工学院 | Electrolysis equipment and application thereof |
| CN114774129A (en) * | 2022-03-29 | 2022-07-22 | 中冶南方都市环保工程技术股份有限公司 | Electrolyte for electrically repairing hexavalent chromium polluted soil and electric repairing method |
| CN114774129B (en) * | 2022-03-29 | 2024-01-23 | 中冶南方都市环保工程技术股份有限公司 | Electrolyte for electrically repairing hexavalent chromium polluted soil and electrically repairing method |
| CN115010122A (en) * | 2022-06-17 | 2022-09-06 | 中钢集团南京新材料研究院有限公司 | Preparation device, preparation method and application of high-oxidation graphene |
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