CN114180560A - Preparation method of coal-based graphene in molten salt system - Google Patents
Preparation method of coal-based graphene in molten salt system Download PDFInfo
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- CN114180560A CN114180560A CN202111573926.6A CN202111573926A CN114180560A CN 114180560 A CN114180560 A CN 114180560A CN 202111573926 A CN202111573926 A CN 202111573926A CN 114180560 A CN114180560 A CN 114180560A
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- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
- C01B32/182—Graphene
- C01B32/184—Preparation
- C01B32/19—Preparation by exfoliation
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2204/00—Structure or properties of graphene
- C01B2204/20—Graphene characterized by its properties
- C01B2204/30—Purity
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2204/00—Structure or properties of graphene
- C01B2204/20—Graphene characterized by its properties
- C01B2204/32—Size or surface area
Abstract
The invention belongs to the field of nano materials, and particularly relates to a preparation method of coal-based graphene in a molten salt system. In order to obtain the graphene with high added value, the preparation method is environment-friendly and low in cost, the affinity of a molten salt system and a carbon material, the intercalation stripping of metal ions and the catalytic action of a transition metal-based catalyst are utilized, and the coal with a disordered structure is converted into the graphene with a regular and ordered structure.
Description
Technical Field
The invention belongs to the field of nano materials, and particularly relates to a preparation method of coal-based graphene in a molten salt system.
Background
As a new two-dimensional layered material in the early century, graphene has important application in various fields such as electrochemical energy storage and conversion, electronic devices, electromagnetic shielding, biological medicine, functional materials and the like by virtue of unique physical and chemical characteristics in various aspects. The preparation and structure control of graphene are always research hotspots. Currently, main methods for preparing graphene include a mechanical exfoliation method, a solution oxidation method, and a chemical vapor deposition method. Among them, the solution oxidation method involves the use of strong acid and strong oxidizer, which not only causes environmental problems but also introduces a large amount of structural defects in the crystal lattice. In addition, the cost of the method is high, and the large-scale application of graphene is limited. Compared with the prior art, the graphene prepared by the chemical vapor deposition method has few defects and high quality, but is limited by a synthesis technology and a processing technology, and the prior method is difficult to meet the requirements of various applications. Therefore, development of an environment-friendly and low-cost method is crucial to synthesis of high-quality graphene in batch.
China is a large coal country, and coal energy plays a significant role in the process of national economic development. From the composition point of view, coal is a complex mixture composed of many high molecular hydrocarbons and a small amount of inorganic minerals, and the main elements are C, H, O, N, S, Al, Si and the like. The carbon content of coal is very high, wherein the carbon content in anthracite reaches 90 percent. From a structural point of view, coal and graphite are similar and present a layered structure. The difference is that the graphite is formed by stacking ordered lamellar layers in structure, the crystallization degree is high, while the coal is formed by graphite microcrystals, the structure is disordered and the defects are more. Coal has dual properties of energy and resources, but at present, the application is mainly based on the energy property, and the research on the resource property is less. When the coal is used as energy fuel, N and S are respectively converted into nitrogen oxide and SO in the combustion process of the coal2. In addition, coal produces many particulate pollutants when incompletely combusted, which can be extremely harmful to the environment. From the perspective of economic benefit and environmental protection, coal is used as a cheap resource, and the method for preparing the high-added-value graphene based on green and efficient development is very significant.
The invention relates to a preparation method of coal-based graphene in a molten salt system, which is green, environment-friendly, simple and feasible, and suitable for batch preparation.
Disclosure of Invention
Aiming at the problems, the invention provides a green, environment-friendly, low-cost and generalizable fused salt synthesis method for preparing coal-based graphene.
In order to achieve the purpose, the invention adopts the following technical scheme:
a preparation method of coal-based graphene in a molten salt system is characterized in that based on the affinity of the molten salt system and anthracite, graphene with few structural defects and high purity is synthesized through intercalation stripping of metal ions and the catalytic action of a transition metal-based catalyst, and comprises the following steps:
and 2, heating the mixed material in an inert atmosphere or vacuum, cooling to room temperature after the reaction is finished, taking out a sample, carrying out acid washing and water washing treatment, and drying to obtain a graphene product.
Further, the molten salt material in the step 1 is a material with good affinity with anthracite.
Further, the molten salt material is one or more of chlorides, carbonates or nitrates of alkali metals and alkaline earth metals, and the recommended material is NaCl, KCl or CaCl2、MgCl2、NaCO3、KCO3、KNO3And the like. The molten salt system has good affinity and strong polarity, and can be fully contacted with anthracite. At higher temperature, molten salt ions can be inserted into the layers of the anthracite coal and stripped to form graphene.
Further, the anthracite coal in the step 1 is subjected to wet grinding or ball milling treatment, and the particle size range is 100 nm-100 microns. The relatively low size of the anthracite coal particle size facilitates the preparation of a uniform graphene product. When the size reaches the micron or even nano scale, the specific surface area of the anthracite particles is improved, the anthracite particles can be more fully contacted with molten salt and a metal catalyst, and the graphene with uniform size, low layer number and high graphitization degree can be obtained.
Further, in the step 1, the precursor of the transition metal catalyst is one or more of chloride, carbonate, acetate, nitrate or sulfate containing iron, cobalt and nickel.
Further, in the step 1, the mass ratio of the molten salt material to the anthracite to the transition metal catalyst precursor is 5-50: 1: 0.5-10, on one hand, the use cost of the catalyst precursor can be reduced, and on the other hand, the specific content needs to be determined according to the catalytic efficiency of the catalyst. When the catalyst exerts catalytic performance, the obtained graphene product has few defects, and the crystallization degree is obviously enhanced.
Further, the inert atmosphere in the step 2 is argon, nitrogen or helium.
Further, the heating treatment in the step 2 specifically comprises: heating to 600-1200 ℃ at a heating rate of 2-50 ℃/min, and reacting for 1-10 h. During the heat treatment, volatile components in the anthracite coal are gradually removed. Meanwhile, when the temperature reaches the melting point or the eutectic point of the salt, the salt begins to be converted into a molten state, free ions can be inserted into the smokeless coal layer, and then the coal can be stripped to form graphene.
Further, nitrogen-containing substances are added into the molten salt material to prepare the nitrogen-doped graphene, and the mass ratio of the nitrogen-containing substances to the anthracite is 1: 0.5 to 10.
Still further, the nitrogen-containing substance is one of urea and melamine.
Compared with the prior art, the invention has the following advantages:
1. the used equipment is simple, and the method is green and efficient;
2. the molten salt can be recycled, the industrial application cost is low, the used salt can be removed from the material in a water washing mode, and then the salt solution is subjected to an evaporation recrystallization process to remove the solvent water, so that the salt can be obtained and recycled;
3. the used chemical reagents are safe, environment-friendly and pollution-free;
4. the graphene prepared in the molten salt system has controllable number and graphitization degree, high purity and no metal impurities.
Drawings
FIG. 1 is a scanning electron micrograph of coal (a) treated in example 1 and coal (b) after ball milling;
fig. 2 is a scanning electron micrograph (a) and a transmission electron micrograph (b) of amorphous graphene prepared in example 2;
fig. 3 is a scanning electron micrograph (a) and a transmission electron micrograph (b) of the graphene prepared in example 3;
FIG. 4 is a Raman spectrum of the coal and the heat-treated coal of examples 1 to 3, amorphous graphene and graphene;
fig. 5 is an N1s XPS spectrum of nitrogen-doped graphene in example 4.
Detailed Description
Example 1:
this example uses anthracite coal subjected to ball milling as a treatment object.
Weighing 2g of anthracite, simultaneously adding 5g of potassium chloride, and uniformly mixing the two. Ethanol is used as a solvent, wet ball milling is adopted, and the ball milling rotation speed and the ball milling time are respectively set to be 600 revolutions per minute and 6 hours. The resulting product was washed 3 times with deionized water and ethanol, respectively, and then dried at 80 ℃ for 12 hours for use. The scanning electron microscope images of the sample before and after ball milling are shown in figure 1, and it can be seen that the size of the coal particles after ball milling is uniform, the particle size is greatly reduced and reaches about 1 micron.
Example 2:
in this example, amorphous graphene prepared in a molten salt was used as a treatment target.
(1) Ball-milling 200mg of anthracite (particle size of 1-10 μm) and 2g K in a ball mill (or mortar)2CO3Fully grinding the mixture until the mixture is uniformly mixed.
(2) And transferring the mixture of the two into a corundum porcelain boat, and putting the corundum porcelain boat into a tube furnace for heat treatment. Argon gas is introduced into the tube furnace, the temperature is increased to 900 ℃ at the speed of 5 ℃/min, and the temperature is kept for 5 h. After the reaction is finished and the temperature is cooled to room temperature, collecting a sample, and using 1mol L-1And (3) treating the graphene oxide by sulfuric acid at 80 ℃ for 8h, washing the graphene oxide by water for 5 times, and drying the graphene oxide (80 ℃, 12h) to obtain an amorphous graphene product.
Scanning electron microscope and transmission electron microscope photographs of amorphous graphene prepared under the conditions are shown in fig. 2, and it can be seen that the molten salt system can successfully convert coal from bulk to sheet graphene, however, the graphitization degree is not very high.
Example 3:
in this example, graphene prepared in a molten salt was used as a treatment target.
(1) 200mg of ball-milled anthracite (particle size 10 to E) is ground by using a ball mill (or mortar)100μm)、2g KCl/CaCl2And 400mg FeCl3Fully grinding the mixture until the mixture is uniformly mixed.
(2) The mixture was transferred to a corundum porcelain boat and heat treated in a tube furnace. Argon gas is introduced into the tube furnace, the temperature is raised to 800 ℃ at the speed of 10 ℃/min, and the temperature is kept for 5 h. After the reaction is finished and the temperature is cooled to room temperature, collecting a sample, removing salt by washing with water, and then adding 1mol L of the solution-1Treating with sulfuric acid at 80 deg.C for 8 hr, washing with water for 5 times, and drying to obtain high purity product.
The scanning electron microscope and the transmission electron microscope of the graphene prepared under the condition are shown in fig. 3, and it can be seen that the surface of a graphene sheet layer is clean and can be curled, the number of the sheet layers is 1-6, and the graphitization degree is high. Fig. 4 is a raman spectrum of different samples, with very low D-peak for graphene treated with transition metal catalyst compared to coal and amorphous graphene. The D, G peak intensity ratio is less than 0.05, which shows that the structural defects are very few, and the further addition of the transition metal catalyst in the molten salt system fully shows that the structural order degree and the crystallinity degree of the graphene can be improved.
Example 4:
in this example, nitrogen-doped graphene prepared in molten salt was used as a treatment target.
(1) 200mg of ball-milled anthracite (particle size 100 nm-10 μm), 2g K, were ground using a ball mill (or mortar)2CO3、400mg FeCl3And 200mg urea were thoroughly ground to mix well.
(2) The mixture was transferred to a corundum porcelain boat and heat treated in a tube furnace. Argon gas is introduced into the tube furnace, the temperature is raised to 800 ℃ at the speed of 2 ℃/min, and the temperature is kept for 4 h. After the reaction is finished and the temperature is cooled to room temperature, collecting a sample, removing salt by washing with water, and then adding 1mol L of the solution-1Treating with sulfuric acid at 80 deg.C for 8 hr, washing with water for 5 times, and drying to obtain high purity product.
An N1s XPS spectrum of the nitrogen-doped graphene prepared under the condition is shown in fig. 5, and it can be seen that the existence forms of the doped N element mainly include graphite nitrogen, pyridine nitrogen and pyrrole nitrogen.
Example 5:
in this example, graphene prepared in a molten salt was used as a treatment target.
(1) Using a ball mill (or mortar) to ball-mill 200mg of anthracite (with the particle size of 1-10 μm) and 1g of KCl/CaCl2、100mg FeCl3Fully grinding the mixture until the mixture is uniformly mixed.
(2) The mixture was transferred to a corundum porcelain boat and heat treated in a tube furnace. Nitrogen gas is introduced into the tube furnace, the temperature is raised to 600 ℃ at the speed of 2 ℃/min, and the temperature is kept for 10 h. After the reaction is finished and the temperature is cooled to room temperature, collecting a sample, removing salt by washing with water, and then adding 1mol L of the solution-1Treating with sulfuric acid at 80 deg.C for 8 hr, washing with water for 5 times, and drying to obtain high purity product.
Example 6:
in this example, graphene prepared in a molten salt was used as a treatment target.
(1) Ball-milling 200mg of anthracite (with the particle size of 1-10 mu m) and 10g of KCl/CaCl by using a ball mill (or a mortar)2And 2g FeCl3Fully grinding the mixture until the mixture is uniformly mixed.
(2) The mixture was transferred to a corundum porcelain boat and heat treated in a tube furnace. Helium gas is introduced into the tube furnace, the temperature is raised to 1200 ℃ at the speed of 50 ℃/min, and the temperature is maintained for 1 h. After the reaction is finished and the temperature is cooled to room temperature, collecting a sample, removing salt by washing with water, and then adding 1mol L of the solution-1Treating with sulfuric acid at 80 deg.C for 8 hr, washing with water for 5 times, and drying to obtain high purity product.
Example 7:
in this example, nitrogen-doped graphene prepared in molten salt was used as a treatment target.
(1) 200mg of ball-milled anthracite (particle size 100 nm-10 μm), 2g K, were ground using a ball mill (or mortar)2CO3、400mg FeCl3And 20mg urea were thoroughly ground to mix well.
(2) The mixture was transferred to a corundum porcelain boat and heat treated in a tube furnace. Argon gas is introduced into the tube furnace, the temperature is raised to 800 ℃ at the speed of 2 ℃/min, and the temperature is maintained for 3 h. To be reversedThe cooling to room temperature should be completed, the sample was collected, the salt was removed by washing with water, and then the solution was cooled to 1mol L-1Treating with sulfuric acid at 80 deg.C for 8 hr, washing with water for 5 times, and drying to obtain high purity product.
Example 8:
in this example, nitrogen-doped graphene prepared in molten salt was used as a treatment target.
(1) 200mg of ball-milled anthracite (particle size 100 nm-10 μm), 2g K, were ground using a ball mill (or mortar)2CO3、400mg FeCl3And 400mg urea were thoroughly ground until well mixed.
(2) The mixture was transferred to a corundum porcelain boat and heat treated in a tube furnace. Argon gas is introduced into the tube furnace, the temperature is raised to 1000 ℃ at the speed of 10 ℃/min, and the temperature is kept for 6 h. After the reaction is finished and the temperature is cooled to room temperature, collecting a sample, removing salt by washing with water, and then adding 1mol L of the solution-1Treating with sulfuric acid at 80 deg.C for 8 hr, washing with water for 5 times, and drying to obtain high purity product.
Claims (10)
1. A preparation method of coal-based graphene in a molten salt system is characterized by comprising the following steps:
step 1, mixing a molten salt material, anthracite and a transition metal catalyst precursor at room temperature, and fully and uniformly grinding all components;
and 2, heating the mixed material in an inert atmosphere or vacuum, cooling to room temperature after the reaction is finished, taking out a sample, carrying out acid washing and water washing treatment, and drying to obtain a graphene product.
2. The method for preparing coal-based graphene in the molten salt system according to claim 1, wherein the molten salt material in the step 1 is a material having good affinity with anthracite.
3. The method for preparing coal-based graphene in the molten salt system according to claim 2, wherein the molten salt material is one or more of chlorides, carbonates or nitrates of alkali metals and alkaline earth metals.
4. The method for preparing coal-based graphene in a molten salt system according to claim 1, wherein the anthracite coal in the step 1 is subjected to wet grinding or ball milling treatment, and the particle size range is 100 nm-100 μm.
5. The method for preparing coal-based graphene in the molten salt system according to claim 1, wherein the precursor of the transition metal catalyst in the step 1 is one or more of chloride, carbonate, acetate, nitrate or sulfate containing iron, cobalt and nickel.
6. The method for preparing coal-based graphene in a molten salt system according to claim 1, wherein the mass ratio of the molten salt material, the anthracite and the transition metal catalyst precursor in the step 1 is 5-50: 1: 0.5 to 10.
7. The method for preparing coal-based graphene in the molten salt system according to claim 1, wherein the inert atmosphere in the step 2 is an argon, nitrogen or helium atmosphere.
8. The method for preparing coal-based graphene in a molten salt system according to claim 1, wherein the heating treatment in the step 2 specifically comprises: heating to 600-1200 ℃ at a heating rate of 2-50 ℃/min, and reacting for 1-10 h.
9. The method for preparing coal-based graphene in a molten salt system according to claim 1, wherein a nitrogen-containing substance is added to the molten salt material to prepare nitrogen-doped graphene, and the mass ratio of the nitrogen-containing substance to anthracite is 1: 0.5 to 10.
10. The method according to claim 9, wherein the nitrogen-containing substance is one of urea and melamine.
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| CN115417401A (en) * | 2022-05-12 | 2022-12-02 | 太原理工大学 | Method for preparing graphene by recoverable low-temperature molten salt |
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