CN107686108B - Method for preparing reduced graphene oxide by dielectric barrier discharge plasma - Google Patents
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- CN107686108B CN107686108B CN201710855342.5A CN201710855342A CN107686108B CN 107686108 B CN107686108 B CN 107686108B CN 201710855342 A CN201710855342 A CN 201710855342A CN 107686108 B CN107686108 B CN 107686108B
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Abstract
the invention relates to a method for preparing reduced graphene oxide by dielectric barrier discharge plasmaAnd (5) processing the daughter bodies for a period of time to obtain a finished product. The invention has the advantages of simple equipment, simple and convenient operation, low energy consumption, no pollution, high production efficiency, carbon source conversion rate of more than 90 percent and specific surface area of 100m of the thermal treatment reduction method2Increase the concentration to 400m2More than g, is a novel preparation method which has low cost, is easy to popularize and is suitable for actual production.
Description
Technical Field
The invention belongs to the technical field of improvement of graphene manufacturing processes, and particularly relates to a method for preparing reduced graphene oxide by using dielectric barrier discharge plasma.
Background
The graphene is formed by sp carbon atoms2The two-dimensional nano material formed by arranging the hybrid tracks according to the honeycomb-shaped crystal lattices has good strength, flexibility, electrical conductivity, thermal conductivity and optical characteristics, and is considered to be a preferred material in the fields of next-generation microelectronic devices, organic photoelectric materials, high-efficiency energy storage materials, multifunctional composite materials, biological medicines and the like.
At present, the method of reducing graphene oxide is considered to be the most feasible method for preparing graphene on a large scale, and specifically includes a chemical reduction method, a photocatalytic reduction method, an electrochemical reduction method, a thermal reduction method and the like. The above methods have respective defects, for example, the reducing agent used in the chemical reduction method has the disadvantages of high pollution and high toxicity, and needs to be removed subsequently, and the operation is complex; the reaction period of the photocatalytic reduction method is longer than 5 hours and a photocatalyst which is difficult to separate is needed; the electrochemical reduction method is carried out in a low-concentration graphene oxide dispersion liquid of 0.1-5 mg/mL, the treatment amount is low, the surface tension of graphene is high, agglomeration is easy to occur, and the formation of reduced graphene with few layers is not facilitated; the thermal reduction method can directly reduce the graphene oxide powder in an inert atmosphere, but needs higher temperature, is difficult to operate, has high requirements on equipment and has high energy consumption.
Through relevant literature retrieval, a small amount of reports of preparing graphene by treating a carbon material with plasma are reported, for example, graphite is treated with plasma in CN102153076A, CN104609408A and CN102781831A, graphene oxide is treated with plasma in CN101993060A, but arc discharge thermal plasma is adopted, the temperature reaches 4000-5000K, the operation is difficult, the requirement on equipment is high, and the energy consumption is high; processing graphite in a hot solution (60-95 ℃) by adopting a plasma polishing technology (CN103484889A) to prepare a graphene solution, wherein the obtained graphene is easy to agglomerate into particles and is not beneficial to application, and the obtained product needs subsequent treatment such as dilution, ultrasound, washing, drying and the like, and the period is as long as 7 hours; the graphene is prepared by treating graphene oxide with microwave plasma (CN102107870A), inductively coupled plasma (CN104085884A) or glow discharge plasma (CN103818899A), so that the equipment is complex and the treatment amount is small.
In addition, the plasma can efficiently decompose carbon source gases such as methane, ethane, acetylene, ethanol, sucrose and the like, and can assist the chemical vapor deposition method to prepare graphene, for example: CN105152165A, CN104773725A, CN103570006A, CN103183334A and CN103708444A, but the method needs to place the substrate in a high temperature region of 300-1000 ℃ and a low pressure of 10-1000 Pa, so the device is complex, the utilization rate of reactants is low, and the yield is low.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides a method for preparing reduced graphene oxide by using dielectric barrier discharge plasma, which is simple and convenient to operate, energy-saving, consumption-saving, environment-friendly and higher in efficiency.
The technical scheme adopted by the invention is as follows:
a method for preparing reduced graphene oxide by dielectric barrier discharge plasma is characterized by comprising the following steps: the method comprises the following steps:
placing graphene oxide between two electrodes in a plasma device;
introducing plasma discharge gas;
⑶, high voltage is applied to the two electrodes, the device generates plasma, and a finished product is obtained after the plasma is treated for a period of time.
the plasma device is a point-plate type, plate-plate type or tube type dielectric barrier discharge device.
the graphene oxide is in a single-layer or multi-layer sheet or powder shape.
the graphene oxide is prepared by a Brodie method, a Staudenmier method, a Hummers method, an Improved-Hummers method, or an Improved method.
and the plasma discharge gas is one or a mixture of air, argon or nitrogen.
Moreover, the conditions of the treatment process were room temperature and normal pressure.
and thirdly, the high voltage is 400-1000V, and the working current is 1-10 amperes.
and step three, the time of high-voltage discharge is 3-60 minutes.
The invention has the advantages and positive effects that:
1. in the method, the reduced graphene oxide is prepared by adopting the dielectric barrier discharge plasma, the product is directly prepared by the raw material one-step method, the operation is simple and convenient, the steps are simple, compared with other methods in the prior art, the treatment time is shortened from more than 7 hours to only within 1 hour, and the efficiency is higher.
2. In the method, other chemical reagents are not introduced in the treatment process, high-temperature heating is not needed, and compared with other methods in the prior art, the method has the advantages of low resource and energy consumption in the treatment process and environmental friendliness.
3. In the method, the plasma formed in the dielectric barrier discharge device contains a large number of electrons, the electrons are attached between each layer of the reduced graphene oxide, and the repulsion force of the electrons enables the reduced graphene oxide to be stripped into single-layer or multi-layer graphene, so that the graphene can be effectively prevented from being aggregated and growing again, and the uniform two-dimensional structure graphene can be formed.
4. The invention has the advantages of simple equipment, simple and convenient operation, low energy consumption, no pollution, high production efficiency and carbon source conversion rate of 90% ofSpecific surface area of 100m from the heat treatment reduction method2Increase the concentration to 400m2More than g, is a novel preparation method which has low cost, is easy to popularize and is suitable for actual production.
Drawings
FIG. 1 is an X-ray powder diffraction pattern of graphene oxide and dielectric barrier discharge reduced graphene oxide (DBD-rGO);
FIG. 2 is a thermogravimetric plot of graphene oxide and dielectric barrier discharge reduced graphene oxide (DBD-rGO);
fig. 3 is an X-ray photoelectron spectrum of graphene oxide and dielectric barrier discharge reduced graphene oxide (DBD-rGO).
Detailed Description
The present invention is further illustrated by the following examples, which are intended to be illustrative, not limiting and are not intended to limit the scope of the invention.
The invention discloses a method for preparing reduced graphene oxide by dielectric barrier discharge plasma, which is characterized by comprising the following steps: the method comprises the following steps:
the method comprises the steps of placing graphene oxide between two electrodes in a plasma device, wherein the plasma device is a point-plate type, plate-plate type or tube type dielectric barrier discharge device, the graphene oxide is in a single-layer or multi-layer sheet shape or powder shape, and the graphene oxide is prepared by a Brodie method, a Staudermaier method, a Hummers method, an Improved-Hummers method or an Improved method.
⑵ introducing plasma discharge gas, wherein the plasma discharge gas is one or a mixture of air, argon or nitrogen.
applying high voltage on the two electrodes, generating plasma by the device, and treating for a period of time to obtain a finished product, wherein the high voltage is 400-1000V, the working current is 1-10A, and the high voltage discharge time is 3-60 minutes.
In the whole treatment process of placing the graphene oxide till the finished product is prepared, the temperature condition is room temperature, and the pressure condition is normal pressure.
The method is completely different from the prior art, and is characterized in that an insulating medium is placed in a gas discharge space to discharge, a non-equilibrium plasma with high electron energy can be generated under normal pressure, and reduced graphene oxide is prepared under the action of high-energy electron bombardment on graphene oxide and the action of redox reaction between active particles and oxygen-containing groups on the graphene oxide in an electric field.
In the reduction process, electrons in the plasma field are adsorbed between each layer of the reduced graphene oxide, the electrons are stripped into single-layer or multi-layer graphene by repulsive force, the preparation process can be directly completed at room temperature, other reagents do not need to be added, the operation is simple, and the preparation period is short.
Example 1
Placing multilayer graphene oxide powder prepared by an Improved method between two electrodes of a plate-plate type dielectric barrier discharge device, introducing argon as discharge gas at room temperature (20-30 ℃), turning on a high-voltage power supply, adjusting the working voltage to 1000V, adjusting the working current to 1.0A, discharging at room temperature for 3min, and performing characterization analysis on the obtained product by XRD, TG and XPS to prove that the graphene oxide is reduced. The carbon source conversion rate in the preparation process is 90 percent, and the specific surface area is 410m2(ii) in terms of/g. The characterization results are shown in fig. 1, 2 and 3, respectively.
Example 2
The preparation method comprises the steps of placing a multilayer graphene oxide sheet prepared by the Staudenmaier method between two electrodes of a plate-plate type dielectric barrier discharge device, introducing nitrogen as discharge gas at room temperature (20-30 ℃), turning on a high-voltage power supply, adjusting the working voltage to 500V, adjusting the working current to 1.0A, discharging at room temperature for 60min, and performing XRD and TG characterization analysis on the obtained product to prove that the graphene oxide is reduced. The carbon source conversion rate in the preparation process is 96 percent, and the specific surface area is 467m2/g。
Example 3
Placing single-layer graphene oxide powder prepared by a Hummers method between two electrodes of a point-plate type dielectric barrier discharge device, introducing air as discharge gas at room temperature (20-30 ℃), turning on a high-voltage power supply, adjusting working voltage to 1000V, adjusting working current to 1.0A, discharging at room temperature for 60min, and performing XRD and TG characterization analysis on the obtained product to prove that the graphene oxide is reduced. The carbon source conversion rate in the preparation process is 92 percent, and the specific surface area is 489m2/g。
Example 4
Placing single-layer graphene oxide powder prepared by an Improved-Hummers method between two electrodes of a tubular dielectric barrier discharge device, introducing argon gas at room temperature (20-30 ℃) to serve as discharge gas, turning on a high-voltage power supply, adjusting working voltage to 500V, adjusting working current to 10A, discharging at room temperature for 60min, and performing characteristic analysis on the obtained product by XRD, TG and the like to prove that the graphene oxide is reduced. In the preparation process, the carbon source conversion rate is 93 percent, and the specific surface area is 595m2/g。
Example 5
Placing single-layer graphene oxide powder prepared by a Brodie method between two electrodes of a tubular dielectric barrier discharge device, introducing air as discharge gas at room temperature (20-30 ℃), turning on a high-voltage power supply, adjusting working voltage to 1000V, adjusting working current to 5.0A, discharging at room temperature for 3min, and performing XRD (X-ray diffraction) and TG (gamma-ray scattering) characterization analysis on the obtained product to prove that the graphene oxide is reduced. Carbon source conversion rate of 93 percent in preparation process, specific surface area of 643m2/g。
Example 6
The multilayer graphene oxide sheet prepared by the Improved method is placed between two electrodes of a tubular dielectric barrier discharge device, nitrogen is introduced as discharge gas at room temperature (20-30 ℃), a high-voltage power supply is turned on, the working voltage is adjusted to 500V, the working current is adjusted to 10A, electricity is discharged at room temperature for 3min, and the obtained product is characterized and analyzed by XRD and TG, so that the reduction of the graphene oxide is proved. In the preparation process, the carbon source conversion rate is 95 percent, and the specific surface area is 756m2/g。
Fig. 1 shows X-ray powder diffraction patterns of graphene oxide, thermally reduced graphene, and dielectric barrier discharge reduced graphene oxide. The peak around 11 ° is assigned to the (001) crystal face of graphene oxide, and this disappearance indicates that graphene oxide is reduced. Compared with an X-ray powder diffraction spectrogram of thermal reduction graphene oxide, the method can find that the peak near 11 degrees of the dielectric barrier discharge reduction graphene oxide completely disappears, and the peak near 23 degrees of the dielectric barrier discharge reduction graphene oxide obviously shifts rightwards and has lower intensity, which indicates that the graphene oxide is reduced into graphene after the dielectric barrier discharge reduction, and the graphene layer obtained by the method has smaller interval and higher reduction degree.
Fig. 2 shows thermogravimetric graphs of graphene oxide, thermally reduced graphene and dielectric barrier discharge reduced graphene oxide. The weight loss of the thermal reduction graphene and the dielectric barrier discharge reduction graphene oxide is obviously lower than that of the graphene oxide, which shows that oxygen-containing functional groups on the reduction graphene oxide are greatly reduced, and the graphene oxide is reduced.
Fig. 3 shows an X-ray photoelectron spectrum of graphene oxide, thermally reduced graphene, and dielectric barrier discharge reduced graphene oxide. For reduced graphene oxide, peaks between 286-289 eV are generally assigned to oxygen-containing groups. In an X-ray photoelectron spectrum of reduced graphene oxide prepared by a dielectric barrier discharge method, a characteristic peak at 286.8eV disappears, and a characteristic peak at 248.5eV is greatly enhanced, which shows that after reduction by dielectric barrier discharge, oxygen-containing functional groups in the graphene oxide are sharply reduced, and the reduction degree is greater than that of thermally reduced graphene oxide.
Claims (4)
1. A method for preparing reduced graphene oxide by dielectric barrier discharge plasma is characterized by comprising the following steps: the method comprises the following steps:
placing graphene oxide between two electrodes in a plasma device;
introducing plasma discharge gas;
thirdly, high voltage is applied to the two electrodes, the device generates plasma, and a finished product is obtained after the plasma is treated for a period of time,
firstly, the graphene oxide is in a single-layer or multi-layer sheet shape or powder shape,
the plasma discharge gas is one or a mixture of air and nitrogen,
the step three is that the high voltage is 400-1000V, the working current is 1-10A,
the conditions of the treatment process are room temperature and normal pressure.
2. the method for preparing reduced graphene oxide by using dielectric barrier discharge plasma according to claim 1, characterized by comprising the step of making the plasma device be a point-plate type, plate-plate type or tubular dielectric barrier discharge device.
3. the method for preparing reduced graphene oxide by using dielectric barrier discharge plasma according to any one of claims 1 or 2, characterized in that the step of preparing the graphene oxide by using a Brodie method, a Staudenmaier method, a Hummers method, an Improved-Hummers method or an Improved method.
4. the method for preparing reduced graphene oxide by using dielectric barrier discharge plasma according to claim 3, wherein the time of high-voltage discharge in the step ⑶ is 3-60 minutes.
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