CN110607174A - Preparation method of graphene carbon dots - Google Patents
Preparation method of graphene carbon dots Download PDFInfo
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- CN110607174A CN110607174A CN201910875773.7A CN201910875773A CN110607174A CN 110607174 A CN110607174 A CN 110607174A CN 201910875773 A CN201910875773 A CN 201910875773A CN 110607174 A CN110607174 A CN 110607174A
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Abstract
The invention discloses a preparation method of graphene carbon dots, which comprises the steps of heating a vitrified carbon material in two sections, preparing an anode material for electrolysis, and finally etching by hydrogen peroxide to obtain the graphene carbon dots with the size of below 20nm and the quantum fluorescence efficiency of 30-60%. The invention takes polyimide, polyacrylonitrile, asphalt and industrial waste thereof or corresponding industrial waste as raw materials, reasonably and efficiently recycles the industrial waste and the waste, and is energy-saving and environment-friendly. The method solves the problem of slag falling of the graphene carbon dots in the preparation process, can prepare a large number of graphene carbon dots with controllable structures, and has controllable carbon dot sizes. The graphene carbon dots prepared by the method can be applied to the aspects of cell marking, fluorescent polymers, fluorescent coatings, tracing detection, damage identification, anticorrosive coatings, material dispersion and the like, and have very wide application prospects.
Description
Technical Field
The invention belongs to the technical field of nano materials, and particularly relates to a preparation method of graphene carbon dots.
Background
Compared with the traditional fluorescent material and other semiconductor carbon dots, the graphene carbon dots are non-toxic, stable in fluorescence, high in intensity and long in luminescence life; and it has more obvious spectral characteristic, can avoid with other spectrum coincidences, has stronger interference killing feature. The light emission spectrum of the carbon dot can change along with the change of the size, so that the fluorescence characteristic can be adjusted by adjusting the size of the carbon dot.
Polyimide is one of organic polymer materials with the best comprehensive performance, resists high temperature of more than 400 ℃, has long-term use temperature range of-200 to 300 ℃, has no obvious melting point on part and high insulating property, and most of the industrial waste of polyimide is treated as garbage at present, thereby being very wasted. However, polyimide industrial waste and its structural analogs (polyacrylonitrile, pitch, carbonizable and graphitizable resins and their industrial waste or corresponding industrial waste) have extremely remarkable sp3 and sp2 bicontinuous features (three-dimensional conductive network) and sp3 surrounds the sp2 feature (two-dimensional) after high-temperature sintering, so that the electrochemical advantages can be fully exploited to etch the sp3 structure and retain the sp2 structure. The method takes the polyimide industrial waste and the structural analogues thereof (polyacrylonitrile, asphalt and the industrial waste or the corresponding industrial waste) as raw materials to prepare the graphene carbon dots, so that the high-performance carbon dots can be prepared, and the aims of waste utilization, energy conservation and environmental protection can be fulfilled.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide a preparation method of graphene carbon dots, which can prepare a large number of graphene carbon dots with controllable structures and controllable sizes.
In order to achieve the purpose, the invention adopts the following technical scheme:
a preparation method of graphene carbon dots comprises the following steps: the method comprises the steps of carrying out two-stage heating treatment on a vitrifiable carbon material, keeping the temperature for a period of time, manufacturing the product into a rod-shaped electrode material, a sheet-shaped electrode material and the like, using the electrode material as a positive electrode for electrolysis, and finally obtaining graphene carbon dots which are dispersed in an electrolyte and have the size of below 20nm and the quantum fluorescence efficiency of 30-60%.
Wherein the heating rate of the first stage heating treatment is 1-60 ℃/min, and the temperature is raised to 400-500 ℃. The temperature rise rate of the second temperature rise treatment is 1-20 ℃/min, and the temperature rises to 800-. After the temperature rise is finished, maintaining the constant temperature for 0.5-6 h.
Further, the electrolyte is one or more of sulfuric acid, ammonium sulfate, ammonia water, sodium sulfate, ammonium chloride and ammonium nitrate, the concentration of the electrolyte is 1-30mol/L, the electrolytic voltage is 10V-100V, and the electrolytic time is 1-24 h.
Further, the vitrifiable carbon materials include polyimides, polyacrylonitriles, asphalts, carbonizable and graphitized resins.
Further, after the electrolysis is finished, hydrogen peroxide with the mass fraction of 1-30% is used for etching to increase the dispersibility and reduce sp3The number of oxygen-containing functional groups is increased while the carbon structure is adopted, and the etching time is 0.5-6 h.
The invention has the advantages that the polyimide industrial waste is used as the raw material, the industrial waste can be recycled, and the energy is saved and the environment is protected. The problem of preparation of the graphene carbon dots is serious slag dropping, and the preparation method adopts a two-stage heating and electrolysis method to prepare the graphene carbon dots, so that the problem of slag dropping can be completely avoided. In the high-temperature growth process of the glassy carbon, in an sp3 structure, a sp2 structure gradually carries out multi-core growth; under electrochemical shearing, the sp3 carbon is sheared, and an sp2 structure surrounded by sp3 carbon is separated from the glassy carbon body, so that a large-size initial graphene carbon dot raw material is obtained; under the action of subsequent strong hydrogen peroxide etching, the sp3 structure in the carbon point is gradually etched and reduced by hydrogen peroxide, so that the purpose of controlling the number of sp3 is achieved. Meanwhile, the size is controllable, the size of the carbon dots is below 20nm, the thickness is below 6nm, and the quantum fluorescence efficiency is between 30 and 60 percent.
Drawings
FIG. 1 is a TEM image of the carbon dots of the graphene prepared in example 1;
FIG. 2 is a fluorescence effect diagram of the graphene carbon dots prepared in example 1;
FIG. 3 is a macro-topography of the graphene carbon dot solution prepared in example 1;
fig. 4 is an AFM image of the carbon dots of the graphenes prepared in example 1.
Detailed Description
Example 1:
heating the polyimide industrial waste to 400 ℃ at the heating rate of 1 ℃/min, then heating to 2000 ℃ at the heating rate of 20 ℃/min, and maintaining the constant temperature for 6 hours; and (3) preparing the product into a rod-shaped positive electrode material, immersing the rod-shaped positive electrode material in 1mol/L ammonium sulfate electrolyte, and electrolyzing for 24 hours at the voltage of 100V.
The graphene carbon dots dispersed in the electrolyte are obtained through the steps, ammonium sulfate is removed through dialysis, and graphene carbon dot dispersion liquid is obtained, wherein the specific properties are shown in table 1. FIG. 1 shows the size of quantum dots of the prepared graphene, which is between 10 and 20nm and has a distinct lattice structure.
The graphene carbon dot dispersion was excited with ultraviolet light, and the graphene carbon dot dispersion exhibited a blue color, as shown in fig. 2. Through a large amount of electrochemical accumulation, the concentration of the quantum dots is gradually increased, a large amount of high-viscosity quantum dot raw materials are finally obtained (figure 3), and the sizes of the graphene quantum dots prepared in a large amount are also uniformly distributed through verification of an atomic force microscope (figure 4).
Example 2:
heating the asphalt industrial waste to 500 ℃ at a heating rate of 60 ℃/min, then heating to 800 ℃ at a heating rate of 1 ℃/min, and maintaining the constant temperature for 0.5 h; preparing the product into a sheet-shaped positive electrode material, immersing the sheet-shaped positive electrode material in an ammonium chloride and ammonia water (m: m is 1:1) electrolyte solution, carrying out electrolysis at the electrolyte concentration of 30mol/L and the voltage of 10V for 1 h; and (3) adding hydrogen peroxide into the electrolyzed electrolyte, wherein the final mass fraction of the hydrogen peroxide is 30%, and etching for 6 h.
The graphene carbon dots dispersed in the electrolyte are obtained through the steps, ammonium chloride, ammonia water and hydrogen peroxide are removed through heating and evaporation, and graphene carbon dot dispersion liquid is obtained, wherein the specific properties of the graphene carbon dot dispersion liquid are shown in table 1.
Example 3:
heating the polyacrylonitrile industrial waste to 450 ℃ at the heating rate of 20 ℃/min, then heating to 1000 ℃ at the heating rate of 15 ℃/min, and maintaining the constant temperature for 2.5 h; preparing the product into a rod-shaped positive electrode material, immersing the rod-shaped positive electrode material in an electrolyte of ammonia water, ammonium nitrate and ammonium chloride (m: m: m is 1:1:1), electrolyzing at the voltage of 50V for 3 hours, wherein the electrolyte concentration is 15 mol/L; and (3) adding hydrogen peroxide into the electrolyzed electrolyte, wherein the final mass fraction of the hydrogen peroxide is 1%, and etching for 0.5 h.
The graphene carbon dots dispersed in the electrolyte are obtained through the steps, ammonia water, ammonium nitrate, ammonium chloride and hydrogen peroxide are removed through heating evaporation and dialysis, and graphene carbon dot dispersion liquid is obtained, wherein the specific properties of the graphene carbon dot dispersion liquid are shown in table 1.
Example 4:
heating polyimide and polyacrylonitrile industrial waste (m: m is 1:1) to 470 ℃ at a heating rate of 40 ℃/min, heating to 1500 ℃ at a heating rate of 12 ℃/min, and maintaining the constant temperature for 4 hours; preparing the product into a sheet-shaped anode material, immersing the sheet-shaped anode material in 20mol/L ammonium chloride electrolyte, and electrolyzing for 5 hours at the voltage of 70V; and adding hydrogen peroxide into the electrolyzed electrolyte dropwise, wherein the final mass fraction of the hydrogen peroxide is 25%, and etching is carried out for 3.5 h.
The graphene carbon dots are obtained through the steps, the graphene carbon dots dispersed in the electrolyte are obtained, ammonium chloride and hydrogen peroxide are removed through heating and evaporation, and graphene carbon dot dispersion liquid is obtained, wherein the specific properties of the graphene carbon dot dispersion liquid are shown in table 1.
Example 5:
heating the polyimide industrial waste to 500 ℃ at a heating rate of 15 ℃/min, then heating to 2000 ℃ at a heating rate of 19 ℃/min, and maintaining the constant temperature for 3.5 h; making the product into a rod-shaped positive electrode material, immersing the rod-shaped positive electrode material in an electrolyte solution of sodium sulfate and ammonium sulfate (m: m is 1:1) (the electrolyte concentration is 8mol/L), electrolyzing at a voltage of 25V for 3.5 h; and (3) adding hydrogen peroxide into the electrolyzed electrolyte, wherein the final mass fraction of the hydrogen peroxide is 5%, and etching for 5.5 h. .
The graphene carbon dots are obtained through the steps, the graphene carbon dots dispersed in the electrolyte are obtained, sodium sulfate, ammonium sulfate and hydrogen peroxide are removed through heating evaporation and dialysis, and graphene carbon dot dispersion liquid is obtained, wherein the specific properties of the graphene carbon dot dispersion liquid are shown in table 1.
Example 6:
heating the polyimide industrial waste to 400 ℃ at the heating rate of 20 ℃/min, heating to 1800 ℃ at the heating rate of 10 ℃/min, and maintaining the constant temperature for 6 hours; and (3) preparing the product into a rod-shaped positive electrode material, immersing the rod-shaped positive electrode material in 10mol/L ammonium nitrate electrolyte, and electrolyzing for 24 hours at the voltage of 100V.
The graphene carbon dots are obtained through the steps, the graphene carbon dots dispersed in the electrolyte are obtained, the ammonium nitrate and the hydrogen peroxide are removed through heating and evaporation, and the graphene carbon dot dispersion liquid is obtained, wherein the specific properties are shown in table 1.
Example 7:
heating the asphalt industrial waste to 500 ℃ at the heating rate of 40 ℃/min, heating to 1400 ℃ at the heating rate of 10 ℃/min, and maintaining the constant temperature for 0.5 h; the product was prepared into a sheet-like positive electrode material, immersed in an electrolyte solution of ammonium chloride and ammonia water (m: m ═ 1:1), and electrolyzed at a voltage of 10V for 1 hour with an electrolyte concentration of 15 mol/L.
The graphene carbon dots are obtained through the steps, the graphene carbon dots dispersed in the electrolyte are obtained, ammonium chloride, ammonia water and hydrogen peroxide are removed through heating and evaporation, and graphene carbon dot dispersion liquid is obtained, wherein the specific properties of the graphene carbon dot dispersion liquid are shown in table 1.
Example 8:
spin-coating glucose on the surface of a nickel plate, heating to 500 ℃ at a heating rate of 40 ℃/min in an inert gas environment, heating to 800 ℃ at a heating rate of 10 ℃/min, and maintaining at a constant temperature for 0.5 h; the product was prepared into a sheet-like positive electrode material, immersed in an electrolyte solution of ammonium chloride and ammonia water (m: m ═ 1:1), and electrolyzed at a voltage of 10V for 1 hour with an electrolyte concentration of 15 mol/L.
The graphene carbon dots are obtained through the steps, the graphene carbon dots dispersed in the electrolyte are obtained, ammonium chloride, ammonia water and hydrogen peroxide are removed through heating and evaporation, and graphene carbon dot dispersion liquid is obtained, wherein the specific properties of the graphene carbon dot dispersion liquid are shown in table 1.
TABLE 1 parameters relating to the examples and comparative examples and the carbon point properties of graphene
As can be seen from the above examples, industrial waste can be effectively utilized and carbon spots can be obtained by the present invention. In addition, the size of the graphene carbon dots can be regulated and controlled in the hydrogen peroxide etching process, and the slower the electrolysis is, the smaller the size of the graphene carbon dots is.
Claims (5)
1. A preparation method of graphene carbon dots is characterized by comprising the following steps: the method comprises the steps of carrying out two-section heating treatment on a vitrifiable carbon material, keeping the temperature for a period of time, manufacturing the product into a rod-shaped electrode material, a sheet-shaped electrode material and the like, using the electrode material as a positive electrode to carry out electrolysis, and finally obtaining graphene carbon dots dispersed in electrolyte.
Wherein the heating rate of the first stage heating treatment is 1-60 ℃/min, and the temperature is raised to 400-500 ℃. The temperature rise rate of the second temperature rise treatment is 1-20 ℃/min, and the temperature rises to 800-. After the temperature rise is finished, maintaining the constant temperature for 0.5-6 h.
2. The method of claim 1, wherein the electrolyte is one or more of sulfuric acid, ammonium sulfate, ammonia water, sodium sulfate, ammonium chloride and ammonium nitrate, and the electrolysis voltage is 1V-100V.
3. The method according to claim 1, characterized in that the vitrifiable carbon material comprises polyimides, polyacrylonitriles, asphalts, carbonizable and graphitizable resins and their industrial waste or corresponding industrial waste products.
4. The method of claim 1, wherein the vitrifiable carbon material comprises carbon material that can be vitrified under catalytic conditions, such as glucose, ethanol, and the like.
5. The method as claimed in claim 1, wherein after the electrolysis is finished, the etching is performed by using hydrogen peroxide with the mass fraction of 1-30% to increase the dispersibility and reduce sp3The number of oxygen-containing functional groups is increased while the carbon structure is adopted, and the etching time is 0.5-6 h.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105565297A (en) * | 2014-10-13 | 2016-05-11 | 徐海波 | Graphene quantum dot prepared from tip surface of carbon fiber through electrochemical oxidation and cutting, and preparation method thereof |
| CN109534334A (en) * | 2019-01-31 | 2019-03-29 | 清华大学深圳研究生院 | Graphene-based electrode material, preparation method and applications |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105565297A (en) * | 2014-10-13 | 2016-05-11 | 徐海波 | Graphene quantum dot prepared from tip surface of carbon fiber through electrochemical oxidation and cutting, and preparation method thereof |
| CN109534334A (en) * | 2019-01-31 | 2019-03-29 | 清华大学深圳研究生院 | Graphene-based electrode material, preparation method and applications |
Non-Patent Citations (3)
| Title |
|---|
| 祖立武: "《化学纤维成型工艺学》", 30 September 2014, 哈尔滨工业大学出版社 * |
| 陈照峰等: "《无机非金属材料学》", 29 February 2016, 西北工业大学出版社 * |
| 高连勋: "《聚酰亚胺纤维》", 31 May 2017, 国防工业出版社 * |
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