CN104058399B - Direct preparation method of high-purity high-quality graphene - Google Patents
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Abstract
The invention discloses a direct preparation method of high-purity high-quality graphene, belonging to the technical field of chemical synthesis. The method takes alkali metal or alkaline earth metal and polyhalogenated hydrocarbon as raw materials, directly prepares the graphene by carrying out metal coupling reaction in a polyhalogenated hydrocarbon body or a benign solvent under an inert environment, and then prepares the high-quality graphene by reacting alcohol, water or acid with the residual active alkali metal or alkaline earth metal; and then carrying out organic solvent washing, acid washing, water washing, filtering, drying and other treatment procedures to obtain the high-purity graphene. The method has the advantages of simple equipment, easy operation, low cost, few byproducts, high yield, high purity and the like, and the prepared graphene is used as a chemical reaction raw material, a conductive material preparation, a catalyst carrier, a battery electrode material, and has wide application prospects in the aspects of physics and microelectronics.
Description
Technical Field
The invention relates to a preparation method of graphene, and belongs to the technical field of graphene chemical synthesis.
Background
Graphene (Graphene) is a new material with a monolayer sheet structure composed of carbon atoms. Is a compound formed by carbon atoms in sp2The hybrid tracks form hexagonal honeycomb lattice planar films with only one carbon atom thick of two-dimensional material. Graphene is currently the thinnest and hardest nanomaterial in the world, and is almost completely transparent, absorbing only 2.3% of light; the heat conductivity coefficient is as high as 5300W/mK, higher than that of carbon nano tube and diamond, its electron mobility is greater than 15000cm 2/V.s at normal temp., and higher than that of carbon nano tube or silicon crystal, and its resistivity is only about 10-6Omega cm, lower than copper or silver, is the material with the smallest resistivity in the world. Because of its extremely low resistivity and high electron transfer rate, it is expected to be used for the development of a new generation of thinner and higher-conduction electronic devices or transistors. Since graphene is essentially a transparent and good conductor, graphene is also suitable for manufacturing transparent touch screens, optical panels, and even solar cellsAnd (4) a pool. Graphene (Graphene) is a novel carbon material that has been extensively studied in recent years.
The application range of the graphene is wide. According to the characteristics of ultra-thin graphene and ultra-high strength, the graphene can be widely applied to various fields, such as ultra-light body armor, ultra-thin and ultra-light aircraft materials and the like. Due to the excellent conductivity, the conductive material also has great application potential in the field of microelectronics. Graphene may be a silicon substitute for fabricating ultra-micro transistors for future super computers, and the higher electron mobility of carbon may enable future computers to achieve higher speed. In addition, the graphene material is an excellent modifier, and can be used as an electrode material auxiliary agent in the field of new energy resources such as supercapacitors and lithium ion batteries due to high conductivity and high specific surface area.
Graphene is the strongest material in the world to date, and it has been estimated that if graphene is used to form a film (thickness of about 100 ten thousand nanometers) having a thickness corresponding to that of a common plastic food packaging bag, it will withstand the pressure of about two tons of heavy articles without breaking; secondly, the method comprises the following steps: graphene is the best conductive material in the world.
The application range of the graphene is wide. According to the characteristics of ultra-thin graphene and ultra-high strength, the graphene can be widely applied to various fields, such as ultra-light body armor, ultra-thin and ultra-light aircraft materials and the like. Due to the excellent conductivity, the conductive material also has great application potential in the field of microelectronics. Graphene may be a silicon substitute for fabricating ultra-micro transistors for future super computers, and the higher electron mobility of carbon may enable future computers to achieve higher speed. In addition, the graphene material is an excellent modifier, and can be used as an electrode material auxiliary agent in the field of new energy resources such as supercapacitors and lithium ion batteries due to high conductivity and high specific surface area.
The research enthusiasm of graphene also attracts the interest of the preparation research of materials at home and abroad, and the preparation methods of the graphene materials have been reported as follows: mechanical exfoliation, chemical oxidation, crystal epitaxial growth, chemical vapor deposition, organic synthesis, and carbon nanotube exfoliation, among others.
Micromechanical lift-off method
In 2004, Geim et al successfully stripped single-layer graphene from highly oriented thermally cracked graphite using a micromechanical stripping process for the first time. The Geim research group successfully prepares the quasi-two-dimensional graphene by using the method and observes the morphology of the quasi-two-dimensional graphene, and discloses the reason for the existence of the two-dimensional crystal structure of the graphene. The micromechanical stripping method can be used for preparing high-quality graphene, but has the defects of low yield and high cost, does not meet the requirements of industrial and large-scale production, and can only be used for small-scale preparation in a laboratory.
Chemical vapor deposition method
The Chemical Vapor Deposition (CVD) method has a new breakthrough in the problem of large-scale preparation of graphene for the first time (refer to the Chemical Vapor Deposition method for preparing high-quality graphene). The CVD method is a process technique in which a reaction substance chemically reacts in a gaseous state to generate a solid substance deposited on the surface of a heated solid substrate, thereby preparing a solid material, and graphene is prepared by the CVD method using Kong of the academy of science and technology, Hong of the university of korea formation university, and Chen of the university of general. They use a simple deposition furnace in the form of a tube with nickel as substrate, into which a gas containing carbon is introduced, such as: and the hydrocarbon is decomposed into carbon atoms at high temperature and is deposited on the surface of the nickel to form graphene, and the graphene film is separated from the nickel sheet through slight chemical etching to obtain the graphene film. The film has the conductivity of 1.1 × 10 at 80% light transmittance6S/m, becomes a potential substitute of the transparent conductive film. High-quality large-area graphene can be prepared by a CVD method, but the price of the ideal substrate material, namely single crystal nickel, is too expensive, which may be an important factor influencing the industrial production of the graphene. The CVD method can meet the requirement of large-scale preparation of high-quality graphene, but has high cost and complex process.
Redox process
The oxidation-reduction method has low preparation cost and is easy to realize, becomes the best method for preparing the graphene, can prepare stable graphene suspension, and solves the problem that the graphene is difficult to prepareThe problem of dispersion. The oxidation-reduction method is to react natural graphite with strong acid and strong oxidizing substances to generate Graphite Oxide (GO), prepare graphene oxide (single-layer graphite oxide) through ultrasonic dispersion, and add a reducing agent to remove oxygen-containing groups on the surface of the graphite oxide, such as carboxyl, epoxy and hydroxyl, to obtain the graphene. After the oxidation-reduction method is proposed, the method becomes the simplest method for preparing graphene in a laboratory by a simple and easy process, and is favored by vast graphene researchers. Ruoff et al found by adding chemicals such as dimethylhydrazine, hydroquinone, sodium borohydride (NaBH)4) And liquid hydrazine or the like to remove the oxygen-containing group of graphene oxide, thereby obtaining graphene. The oxidation-reduction method can prepare stable graphene suspension, and solves the problem that graphene is difficult to disperse in a solvent. The oxidation-reduction method has the disadvantages that the macro preparation is easy to cause waste liquid pollution, and the prepared graphene has certain defects, such as topological defects of five-membered rings, seven-membered rings and the like or structural defects of-OH groups, which cause the loss of partial electrical properties of the graphene, so that the application of the graphene is limited.
Solvent stripping process
The principle of the solvent stripping method is that a small amount of graphite is dispersed in a solvent to form a low-concentration dispersion liquid, van der waals force between graphite layers is destroyed by the action of ultrasonic waves, and the solvent can be inserted between the graphite layers to carry out layer-by-layer stripping, so that the graphene is prepared. The method does not damage the structure of the graphene like an oxidation-reduction method, and can prepare high-quality graphene. The yield of graphene in N-methylpyrrolidone is highest (about 8%), and the conductivity is 6500S/m. Researches find that the high-orientation thermal cracking graphite, the thermal expansion graphite and the microcrystalline artificial graphite are suitable for preparing the graphene by a solvent stripping method. The solvent stripping method can be used for preparing high-quality graphene, no defect is introduced on the surface of the graphene in the whole liquid phase stripping process, and wide application prospects are provided for the application of the graphene in the fields of microelectronics, multifunctional composite materials and the like. The disadvantage is the low yield.
Solvothermal process
The solvothermal method is an effective method for preparing a material by heating a reaction system to a critical temperature (or a temperature close to the critical temperature) and generating high pressure in the reaction system in a specially-made closed reactor (autoclave) by using an organic solvent as a reaction medium. The solvothermal method solves the problem of large-scale preparation of graphene, and brings negative effects of low conductivity. In order to overcome the defects caused by the method, researchers combine a solvothermal method and a redox method to prepare high-quality graphene. Dai et al found that the resistance of the graphene film prepared by reducing graphene oxide under solvothermal conditions was less than that of graphene prepared under conventional conditions. The solvothermal method has attracted more and more attention by scientists due to the characteristic that high-quality graphene can be prepared under a high-temperature and high-pressure closed system.
Other methods
The preparation method of the graphene also comprises a high-temperature reduction method, a light reduction method, an epitaxial crystal growth method, a microwave method, an electric arc method, an electrochemical method and the like. At present, the production method of graphene mainly comprises a mechanical stripping method and a thermal expansion graphite method. Among them, the mechanical exfoliation method is to repeatedly bond and exfoliate expensive highly oriented pyrolytic graphite with an adhesive tape and finally transfer it onto the surface of a base material. The method has low efficiency, small yield and high cost, and can only be limited to laboratory production. The thermal expansion graphite method has complex steps and large damage to the graphene structure. The method for preparing high-quality graphene by combining the polyhalogenated hydrocarbon with the redox method through the coupling reaction of the active metal is provided on the basis of the various methods, the method is rich in raw materials, green and environment-friendly, and a novel method for large-scale production can be realized.
Disclosure of Invention
The invention aims to overcome the problems in the prior art and provides the method which is simple, environment-friendly in process, low in cost and capable of preparing high-quality graphene in a large scale.
The invention discloses a direct preparation method of high-purity high-quality graphene, belonging to the technical field of chemical synthesis. The method takes alkali metal or alkaline earth metal and polyhalogenated hydrocarbon as raw materials, and carries out metal coupling reaction in polyhalogenated hydrocarbon body or benign solvent under inert environment, wherein the molar ratio of the metal to the polyhalogenated hydrocarbon is preferably between 0.5 and 30; reacting at 0-300 ℃ for 0.1-72 hours to obtain a graphene crude product, removing residual alkali metal or alkaline earth metal by using water, alcohol or acid to prepare high-quality graphene, and washing by using an organic solvent, acid washing, water washing, filtering and drying to obtain the high-purity high-quality graphene. The method has the advantages of simple method, easy operation, low cost, few byproducts, high yield, high purity and the like, and the graphene has wide application prospect in the aspects of physics and microelectronics as a chemical reaction raw material, a conductive material preparation, a catalyst carrier and a battery electrode material.
The invention relates to a direct preparation method of high-purity high-quality graphene, which is characterized in that active alkali metal or alkaline earth metal and polyhalogenated hydrocarbon are used as raw materials, and the high-purity high-quality graphene is directly prepared through metal coupling reaction of the halogenated hydrocarbon, and comprises the following steps:
(1) under the protection of inert gas, dispersing active alkali metal or alkaline earth metal in a polyhalogenated hydrocarbon body or a benign solvent thereof for coupling reaction, or dropwise adding or supplementing the polyhalogenated hydrocarbon body or a solution thereof into an active alkali metal or alkaline earth metal reaction system, and carrying out coupling reaction in a closed container at the temperature of 0-300 ℃ for 0.1-72 hours to prepare a suspension of a crude graphene product;
(2) adding alcohol, water or acid into the suspension to react with the residual active alkali metal or alkaline earth metal to prepare high-quality graphene;
(3) and filtering the mixture, washing the mixture with an organic solvent, pickling, washing with water, filtering, drying, and removing the solvent and by-products of the graphene crude product in the suspension solution to obtain the high-purity graphene.
The method according to claim 1, wherein the polyhalogenated hydrocarbon is a polyhalogenated aromatic hydrocarbon, a polyhalogenated condensed cyclic hydrocarbon or a mixture thereof, and the structural formula is shown in fig. 1, wherein X groups are F, Cl, Br, I atoms, trihalovinyl groups or pentahalophenyl groups, X groups are halogen atoms or groups of the same or different types, and the polyhalogenated hydrocarbon is: tetrabromo (fluoro, chloro or iodo) ethylene, hexabromo (fluoro, chloro or iodo) 1, 3-butadiene; hexabromo (fluoro, chloro or iodo) benzene, trichlorotribromo (fluoro or iodo) benzene; octachloro (fluoro, bromo or iodo) naphthalene, tetrachlorotetrabromo (fluoro or iodo) naphthalene; decachloro (fluoro, bromo or iodo) anthracene (phenanthrene), hexabromo (iodo) tetrachloranthracene (phenanthrene), hexachlorotetrabromoanthracene (phenanthrene); such as decachloro (fluoro, bromo, iodo) pyrene, hexabromotetrachloropyrene, tetrabromohexachloropyrene; perchloro (fluoro, bromo, iodo) biphenyl, perchloro (bromo, iodo) terphenyl, polychlorinated (bromo, iodo) benzanthracene (pyrene), etc., most preferably one or more mixtures of tetrabromo (chloro) ethylene, hexabromo (chloro or fluoro) benzene, octabromo (chloro or fluoro) naphthalene, decabromo (chloro or fluoro) anthracene (phenanthrene), decabromo (chloro or fluoro) pyrene, perchloro (bromo) biphenyl.
The method according to claim 1, wherein the alkali metal or alkaline earth metal is selected from one or more of active metals lithium, sodium, potassium, magnesium, calcium, strontium, barium and lanthanum, and most preferably from one or more of lithium, sodium, potassium and magnesium.
The process according to claim 1, wherein the polyhalogenated hydrocarbon solvent is selected from the group consisting of solvents which do not react with the alkali metal or alkaline earth metal and polyhalogenated hydrocarbon, and is C5-C20 alkane, C1-C16 ether (simple ether or mixed ether), C1-C5 alkyl-substituted aromatic hydrocarbon or acetal solvent, and is specifically paraffin oil, (methyl, ethyl) tetrahydrofuran, dioxane, ethyl (propane, butane, pentane, hexane) ether, ethyl-propylene (butane, pentane, hexane) ether, propyl (butane, pentane, hexane) ether, (tri-, di-, mono-, di-or tri-) ethylene (propane, butane) glycol dimethyl (ethane, propane, butane, benzene) ether, benzyl (ethane, propane, butane) ether, diphenyl ether, dimethyl (ethane, propane, butane) phenyl ether, benzyl ether, glycerol ether, eicosane, ethyl, propane, butane) benzene, dimethyl (ethane, dimethyl ether, etc, One or more of C, T) benzene, trimethyl (B, C, T) benzene, biphenyl and dimethyl biphenyl.
The process according to claim 1, wherein the molar ratio between the alkali metal or alkaline earth metal and the polyhalogenated hydrocarbon is in the range of 0.1 to 100, most preferably in the range of 0.5 to 30.
The method according to claim 1, wherein the polyhalogenated hydrocarbon or the solution thereof is directly mixed with the active metal for reaction, or the polyhalogenated hydrocarbon or the solution thereof is added dropwise or supplemented into the reaction solution of the active metal along with the reaction, or the polyhalogenated hydrocarbon or the solution thereof is added with or supplemented with the active metal for coupling reaction.
The method according to claim 1, wherein the alcohol, water or acid used for reducing or eliminating the residual alkali metal or alkaline earth metal is one or more selected from methanol, ethanol, propanol, isopropanol, n-butanol, ethylene glycol, propylene glycol, glycerol, water, hydrochloric acid, hydrobromic acid, hydroiodic acid, hydrofluoric acid, sulfuric acid, phosphoric acid, nitric acid, oxalic acid, formic acid and acetic acid, and the residual alkali metal or alkaline earth metal is reacted with the remaining alkali metal or alkaline earth metal to obtain high-quality graphene.
The method according to claim 1, wherein the organic solvent is selected from the group consisting of petroleum ether, acetone, ether, ethanol, methanol, DMAc and DMF, the solvent is selected from the group consisting of methanol, ethanol, acetic acid, hydrochloric acid, hydrobromic acid, hydroiodic acid, hydrofluoric acid, sulfuric acid, nitric acid, oxalic acid, formic acid and acetic acid, the residual salt is removed by washing with deionized water, and the graphene is dried and stored to obtain the high purity graphene.
The method of claim 1, wherein the reaction is carried out at a temperature in the range of 0 ℃ to 300 ℃, most preferably 30 ℃ to 180 ℃; however, when tetrachloroethylene, hexachlorobenzene, bromobenzene or tetrabromoethylene are coupled with metallic sodium, the reaction temperature is limited to 120 ℃ or lower, i.e., the metallic sodium coupling reaction in the range of 120 ℃ to 400 ℃ is excluded.
The process according to claim 1, wherein the reaction pressure is in the range of 0.1 to 5MPa, and the reaction is carried out under normal pressure or pressurized reaction conditions corresponding to the activities of the metal and the polyhalogenated hydrocarbon as the raw materials, but the reaction is limited to normal pressure when the polyhalogenated hydrocarbon is hexachlorobenzene.
The preparation method of the graphene has the following advantages:
1. the reaction can be carried out under the conditions of normal pressure and low temperature, the equipment is simple, the operation is easy, the process steps are few, and the large-scale industrial production is easy to carry out;
2. the method has the advantages of low raw material cost, less byproducts and recyclable solvent, and is an atom-economical environment-friendly synthesis method;
3. the reaction yield is high, even can reach 100%, the product quality is high, the conductivity is strong;
based on the advantages, the graphene provided by the invention has a wide application prospect in the aspects of chemical reaction raw materials, conductive film preparation, catalyst carriers, battery electrode materials, physics and microelectronics.
Description of the drawings:
FIG. 1 synthesis of polyhalogenated hydrocarbon unit structures of graphene;
fig. 2 scanning electron microscope photograph of graphene;
figure 3 EDS spectra data for graphene;
figure 4 XRD spectroscopy data for graphene;
fig. 5 graphene BET specific surface test (ASAP 2010).
Detailed Description
The invention is described in further detail below with reference to the figures and specific embodiments.
The methods used in the following examples are conventional unless otherwise specified, but the present examples are repeated with special attention to the risk of detonation and explosion, without expert or skilled workers, and with the care of the researchers with a great deal of experience.
The specific method for preparing graphene in this embodiment includes the following steps.
Example 1 Synthesis of graphene
Adding 100mL of toluene, 3.0g of sodium metal and 6.0g of hexabromobenzene into a clean and dry reaction kettle, carrying out reflux reaction for 8 hours under the condition of argon protection, stopping heating, cooling to room temperature to obtain a black graphene suspension, adding 30 mL of absolute ethyl alcohol, stirring for reaction for 2 hours, carrying out vacuum filtration to obtain a crude graphene product, cleaning for 3 times with acetone, washing for 3 times with water, washing for 2 times with 10% hydrochloric acid, washing for multiple times with water to be neutral, and carrying out vacuum drying to obtain a pure graphene product.
Example 2 Synthesis of graphene
Adding 10mL of dimethylbenzene and 50mL of tetrahydrofuran, 3.0g of sodium metal and 6.0g of hexabromobenzene into a clean and dry reaction kettle, after refluxing reaction for 10 hours, stopping heating, cooling to room temperature to obtain a black graphene suspension, then adding 30 mL of anhydrous methanol, stirring and reacting for 2 hours, carrying out vacuum filtration to obtain a crude graphene product, cleaning with acetone for 3 times, washing with water for 3 times, washing with 10% sulfuric acid for 2 times, washing with water for multiple times to be neutral, and carrying out vacuum drying to obtain a pure graphene product.
Example 3 Synthesis of graphene
Adding 100mL of diphenyl ether, 3.0g of metal sodium and 5.0g of hexabromobenzene into a clean and dry reaction kettle, reacting for 8 hours at 110 ℃, stopping heating, cooling to room temperature to obtain a black graphene suspension, adding 30 mL of absolute ethyl alcohol, stirring for reacting for 2 hours, carrying out vacuum filtration to obtain a crude graphene product, cleaning for 3 times with acetone, washing for 3 times with water, pickling for 2 times with 10% hydrochloric acid, washing for multiple times with water to be neutral, and carrying out vacuum drying to obtain a pure graphene product.
Example 4 Synthesis of graphene
Adding 100mL of tetrahydrofuran, 3.0g of metal potassium and 4.0g of hexabromobenzene into a clean and dry reaction kettle, performing reflux reaction for 10 hours, stopping heating, cooling to room temperature to obtain a black graphene suspension, adding 25 mL of methanol, performing stirring reaction for 2 hours, performing vacuum filtration to obtain a crude graphene product, cleaning with acetone for 3 times, washing with water for 3 times, washing with 10% hydrochloric acid for 2 times, washing with water for multiple times to be neutral, and performing vacuum drying to obtain a pure graphene product.
Example 5 Synthesis of graphene
Adding 100mL of tetrahydrofuran, 3.0g of metal potassium and 4.0g of decabromoanthracene into a clean and dry reaction kettle, performing reflux reaction for 10 hours, stopping heating, cooling to room temperature to obtain a black graphene suspension, adding 50mL of ethanol, stirring for reaction for 2 hours, performing vacuum filtration to obtain a crude graphene product, cleaning with diethyl ether for 3 times, washing with water for 3 times, washing with 10% hydrochloric acid for 2 times, washing with water for multiple times to be neutral, and performing vacuum drying to obtain a pure graphene product.
Example 6 Synthesis of graphene
Adding 100mL of dimethylbenzene, 5.0g of metal potassium, 2.0g of tetrabromoethylene, 2.0g of hexabromobenzene and 4.0g of decabromopyrene into a clean and dry reaction kettle, performing reflux reaction for 10 hours, stopping heating, cooling to room temperature to obtain black graphene suspension, adding 30 mL of anhydrous methanol, stirring for reaction for 2 hours, performing vacuum filtration to obtain a crude graphene product, cleaning with diethyl ether for 3 times, washing with water for 3 times, washing with 10% hydrochloric acid for 2 times, washing with water for multiple times until the solution is neutral, and performing vacuum drying to obtain a pure graphene product.
Example 7 Synthesis of graphene
Adding 100mL of trimethylbenzene, 6.0g of sodium metal, 5.0g of hexabromobenzene, 2.0g of hexachlorobenzene and 4.0g of decabromoanthracene into a clean and dry reaction kettle, performing reflux reaction for 10 hours, stopping heating, cooling to room temperature to obtain a black graphene suspension, adding 30 mL of absolute ethyl alcohol, stirring for reaction for 2 hours, performing vacuum filtration to obtain a graphene crude product, cleaning with diethyl ether for 3 times, washing with water for 3 times, washing with 10% hydrochloric acid for 2 times, washing with water for multiple times until the graphene crude product is neutral, and performing vacuum drying to obtain a pure graphene product.
Example 8 Synthesis of graphene
Adding 100mL of diphenyl ether, 3.0g of lithium metal, 5.0g of hexabromobenzene and 4.0g of decabromophenanthrene into a clean and dry reaction kettle, performing reflux reaction for 10 hours, stopping heating, cooling to room temperature to obtain a black graphene suspension, adding 30 mL of absolute ethyl alcohol, stirring for reaction for 2 hours, performing vacuum filtration to obtain a graphene crude product, cleaning with diethyl ether for 3 times, washing with water for 3 times, washing with 10% hydrochloric acid for 2 times, washing with water for multiple times until the graphene crude product is neutral, and performing vacuum drying to obtain a pure graphene product.
Example 9 Synthesis of graphene
Adding 100mL of tetrahydrofuran, 7.0g of metal potassium, 5.0g of hexabromobenzene and 4.0g of decabromopyrene into a clean and dry reaction kettle, performing reflux reaction for 10 hours, stopping heating, cooling to room temperature to obtain a black graphene suspension, adding 30 mL of absolute ethyl alcohol, stirring for reaction for 2 hours, performing vacuum filtration to obtain a crude graphene product, cleaning with diethyl ether for 3 times, washing with water for 3 times, washing with 10% hydrochloric acid for 2 times, washing with water for multiple times until the crude graphene product is neutral, and performing vacuum drying to obtain a pure graphene product.
Example 10 Synthesis of graphene
Adding 100mL of dioxane, 6.0g of metal magnesium, 6.0g of hexabromobenzene, 4.0g of decabromoanthracene and 2.0g of decabromopyrene into a clean and dry reaction kettle, performing reflux reaction for 10 hours, stopping heating, cooling to room temperature to obtain a black graphene suspension, adding 30 mL of absolute ethyl alcohol, stirring for reaction for 2 hours, performing vacuum filtration to obtain a crude graphene product, washing with diethyl ether for 3 times, washing with water for 3 times, washing with 10% hydrochloric acid for 2 times, washing with water for multiple times to be neutral, and performing vacuum drying to obtain a pure graphene product.
Example 11 Synthesis of graphene
100mL of diethylene glycol dimethyl ether, 4.0g of tetrabromoethylene, 6.0g of metal potassium, 6.0g of hexabromobenzene, 4.0g of decabromoanthracene and 2.0g of decabromopyrene are added into a clean and dry reaction kettle, after reflux reaction for 10 hours, heating is stopped, the mixture is cooled to room temperature to obtain black graphene suspension, then 30 mL of absolute ethyl alcohol is added, after stirring reaction for 2 hours, the crude graphene product obtained by decompression and suction filtration is washed by ethyl ether for 3 times, washed by water for 3 times and washed by 10% hydrochloric acid for 2 times, then washed by water for multiple times until the crude graphene product is neutral, and the pure graphene product is obtained by vacuum drying.
Example 12 Synthesis of graphene
Adding 100mL of diphenyl ether, 2.0g of tetrachloroethylene, 6.0g of metal potassium, 6.0g of hexaiodobenzene, 3.0g of decabromoanthracene and 1.0 g of decabromopyrene into a clean and dry reaction kettle, carrying out reflux reaction for 10 hours, stopping heating, cooling to room temperature to obtain a black graphene suspension, adding 30 mL of absolute ethyl alcohol, stirring for reaction for 2 hours, carrying out vacuum filtration to obtain a crude graphene product, washing with diethyl ether for 3 times, washing with water for 3 times, washing with 10% hydrochloric acid for 2 times, washing with water for multiple times to be neutral, and carrying out vacuum drying to obtain a pure graphene product.
Example 13 Synthesis of graphene
Adding 100mL of diphenyl ether, 2.0g of tetrachloroethylene, 6.0g of metal potassium, 6.0g of hexabromobenzene, 3.0g of decabromoanthracene and 1.0 g of decabromobiphenyl into a clean and dry reaction kettle, performing reflux reaction for 10 hours, stopping heating, cooling to room temperature to obtain black graphene suspension, adding 30 mL of absolute ethyl alcohol, stirring for reaction for 2 hours, performing vacuum filtration to obtain a crude graphene product, washing with diethyl ether for 3 times, washing with water for 3 times, washing with 10% hydrochloric acid for 2 times, washing with water for multiple times to be neutral, and performing vacuum drying to obtain a pure graphene product.
Example 14 Synthesis of graphene
100mL of diphenyl ether, 8.0g of metal potassium, 2.0g of carbon tetrachloride, 2.0g of tetrachloroethylene, 6.0g of hexaiodobenzene, 3.0g of decabromoanthracene and 1.0 g of all-bromo terphenyl are added into a clean and dry reaction kettle, after reflux reaction for 10 hours, heating is stopped, the mixture is cooled to room temperature to obtain black graphene suspension, then 30 mL of absolute ethyl alcohol is added, after stirring reaction for 2 hours, the crude graphene product obtained by decompression suction filtration is washed by ethyl ether for 3 times, washed by water for 3 times and washed by 10% hydrochloric acid for 2 times, washed by water for multiple times until the crude graphene product is neutral, and the pure graphene product is obtained by vacuum drying.
The graphene crystal grains prepared in example 1 were examined by the following method.
1. Graphene crystal grain Scanning Electron Microscope (SEM) and X-ray energy spectrometer characterization detection
The graphene crystal grains prepared in example 1 are characterized and detected by a Scanning Electron Microscope (SEM), and the method is as follows: taking a small amount of graphene black powder, performing ultrasonic dispersion in absolute ethyl alcohol, then taking 1-2 drops of graphene black powder to drop on a sample table, airing and spraying gold, then observing the prepared graphene crystal grain structure by a scanning electron microscope, and simultaneously testing EDAX data of the graphene crystal grain structure as shown in figure 2 and figure 3: as can be seen from the scanning electron microscope photograph of the graphene crystal grain in fig. 2, the size of the graphene crystal grain structure prepared by the method of the present invention can reach below micron level; fig. 3 is the energy spectrum data, and it can be seen that the graphene crystal grains are mainly composed of element C and residual halogen, the carbon atom content is 90.26%, and the residual halogen atom content is 3.97%.
2. Graphene crystal grain XRD characterization detection
Graphene grain XRD characterization detection is carried out on the graphene prepared in example 1, and as shown in FIG. 4, a characteristic absorption peak of the graphene with 2 theta between 15 and 35 can be seen from an XRD pattern of the graphene grains.
BET specific surface test
Adopt N2As an adsorbed gas, the graphene crystal grains prepared in example 1 were subjected to BET specific surface test (ASAP 2010). As shown in FIG. 5, the BET specific surface area of the obtained graphene crystal grains is 1.37m2The total pore volume is 0.013mL/g, and the average pore diameter is 32.9 nm.
Claims (5)
1. A direct preparation method of high-purity high-quality graphene is characterized in that active alkali metal or alkaline earth metal and polyhalogenated hydrocarbon are used as raw materials, and the high-purity high-quality graphene is directly prepared through metal coupling reaction of the halogenated hydrocarbon, and comprises the following steps:
(1) under the protection of inert gas, dispersing active alkali metal or alkaline earth metal in a polyhalogenated hydrocarbon benign solvent for coupling reaction, and performing coupling reaction in a closed container at the temperature of 0-300 ℃ for 0.1-72 hours to prepare suspension of a graphene crude product; under the condition of normal pressure reflux reaction;
(2) adding alcohol, water or acid into the suspension to react with the residual active alkali metal or alkaline earth metal to prepare high-quality graphene;
(3) filtering the mixture, washing the mixture with an organic solvent, pickling, washing with water, filtering, and drying to remove the solvent and by-products of the graphene crude product in the suspension solution, thereby obtaining high-purity graphene;
the polyhalogenated hydrocarbon is: tetrabromo (fluoro, chloro or iodo) ethylene, hexabromo (fluoro, chloro or iodo) 1, 3-butadiene; hexabromo (fluoro, chloro or iodo) benzene, trichlorotribromo (fluoro or iodo) benzene; octachloro (fluoro, bromo or iodo) naphthalene, tetrachlorotetrabromo (fluoro or iodo) naphthalene; decachloro (fluoro, bromo or iodo) anthracene (phenanthrene), hexabromo (iodo) tetrachloranthracene (phenanthrene), hexachlorotetrabromoanthracene (phenanthrene); decachloro (fluoro, bromo, iodo) pyrene, hexabromotetrachloropyrene, tetrabromohexachloropyrene; perchloro (fluorine, bromine, iodine) biphenyl, perchloro (bromine, iodine) terphenyl, polychlorine (bromine, iodine) benzanthracene (pyrene);
the benign solvent is selected from a solvent which does not react with the raw materials of alkali metal or alkaline earth metal and polyhalogenated hydrocarbon, and is one or a mixture of more of (methyl, ethyl) tetrahydrofuran, dioxane, (triscondensation, disunion, monocondensation) ethylene (propylene, butylene) glycol dimethyl (ethylene, propylene, butylene, benzene) ether, diphenyl ether, dimethyl (ethylene, propylene, butylene) phenyl ether and benzyl ether.
2. The preparation method according to claim 1, wherein the alkali metal or alkaline earth metal is selected from one or more of active metals of lithium, sodium, potassium, magnesium, calcium, strontium and barium.
3. The method according to claim 1, wherein the alcohol, water or acid used for reducing or eliminating the residual alkali metal or alkaline earth metal is one or more selected from the group consisting of methanol, ethanol, propanol, isopropanol, n-butanol, ethylene glycol, propylene glycol, glycerol, water, hydrochloric acid, hydrobromic acid, hydroiodic acid, hydrofluoric acid, sulfuric acid, phosphoric acid, nitric acid, oxalic acid, formic acid and acetic acid.
4. The method of claim 1, wherein the organic solvent is one or more selected from petroleum ether, acetone, diethyl ether, ethanol, methanol, DMAc and DMF, and is used for washing residual reaction solvent, the washing acid used for acid washing is one or more selected from hydrochloric acid, hydrobromic acid, hydroiodic acid, hydrofluoric acid, sulfuric acid, phosphoric acid, nitric acid, oxalic acid, formic acid and acetic acid, and the water washing is performed by washing residual salt with deionized water.
5. The method of claim 1, wherein the coupling reaction temperature is from 30 ℃ to 180 ℃.
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