CN113387351B - Preparation process for preparing three-dimensional porous graphene at low cost - Google Patents
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Abstract
The invention belongs to the field of carbon nano materials, and particularly relates to a preparation process for preparing three-dimensional porous graphene at low cost. The carbon source selected by the invention is the waste coal gangue as a basic raw material, so that the waste coal gangue is recycled, the material can be saved, and the energy consumption can be reduced. The metal catalyst is added, so that the graphitization process is accelerated, the temperature of graphite is reduced, the graphitization degree is increased, the interlayer spacing is increased, intercalation is easier, and the quality of the peeled graphene is higher. The graphene oxide aqueous solution is used as a precursor for in-situ self-assembly, so that stacking among graphene sheets is effectively reduced, and the excellent performance of graphene is maintained. The three-dimensional porous graphene with higher quality is prepared from a low-cost carbon source by adopting a low-cost preparation process, can be prepared in a large quantity, and is beneficial to the research and development of downstream products of the three-dimensional porous graphene: pollutant adsorption, resistance type gas sensors, lithium ion batteries, supercapacitors, modified cement concrete, and the like.
Description
Technical Field
The invention belongs to the field of carbon nano materials, and particularly relates to a preparation process for preparing three-dimensional porous graphene at low cost.
Background
In 2004, andre Geim and Konstantin Novoselov first exfoliated graphene from graphite, which was a kind of graphene-free material with sp 2 Two-dimensional nanomaterial of infinite six-membered ring units formed by hybridized C atoms in covalent bond form. Graphene is considered as the basic constituent unit of all other dimensional carbon nanomaterials, and can be wrapped into zero-dimensional fuschileren bodies, curled into one-dimensional carbon nanotubes and stacked into three-dimensional graphite. The graphene has the highest strength (1.0 TPa), the highest tensile strength (130 GPa) and the largest specific surface area (2630 m) 2 /g), etc. In addition, graphene has electron mobility up to 15000cm at room temperature 2 and/V, the heat conductivity coefficient is as high as 3000-5000 w/(m.K). Graphene attracts attention of various students at home and abroad by virtue of excellent performance, and becomes a research hotspot at one time.
However, graphene is extremely easy to agglomerate due to pi-pi stacking effect and strong van der Waals force between sheets, so that the specific surface area is greatly reduced, the mechanical property and conductivity of the graphene are greatly reduced, and the exertion of excellent properties is severely limited. One of the strategies for solving the problems is to construct porous three-dimensional reticular graphene, and the three-dimensional porous graphene not only maintains the excellent performance of graphene, but also has the advantages of low density, high specific area, high porosity, low thermal conductivity and the like, and can be widely applied to various fields of photonics, catalysis, batteries, supercapacitors, biosciences and the like.
Graphene and its derivatives have once become a focus of attention for researchers due to their excellent properties, but their preparation costs are expensive, greatly limiting the development of their downstream products. For this reason, a preparation process for preparing graphene and its derivatives at low cost is urgently sought. At present, the main preparation raw materials of the graphene and the derivatives thereof are prepared by taking carbon powder as the raw materials, but the price of the carbon powder is high and reaches 5000-8000 yuan/ton, and the price of the carbon powder as a strategic reserve resource is still rising. Coal is the fossil fuel with the most abundant reserve and the most widely distributed regions on the earth. The elements forming the coal organic matters mainly comprise carbon, hydrogen, oxygen, nitrogen, sulfur and the like, wherein the carbon, the hydrogen and the oxygen are the main bodies of the coal organic matters and account for more than 95 percent; and the deeper the coalification degree, the higher the carbon content and the lower the hydrogen and oxygen contents. This determines that coal is a raw material for preparing graphene and its derivatives.
Gangue is a waste carbon source associated in the coal resource exploitation process, is a mixture of carbonaceous, argillaceous and sandy shale, has a low calorific value, contains 20% -30% of carbon and some humic acid. Coal gangue has been stored at about 1000Mt in the past year in China, and is still continuously discharged at about 100Mt each year, so that not only is the coal gangue accumulated in the ground occupied, but also air pollution can be caused by spontaneous combustion or fire disaster can be caused. The inherent carbon content of the gangue can be used as a preparation raw material of graphene and derivatives thereof, and the treatment of the gangue accords with the recycling of solid wastes.
Disclosure of Invention
In order to solve the problems in the prior art, a preparation process for preparing the three-dimensional porous graphene with low cost is provided, waste coal gangue is used as a carbon source, the defects of the existing preparation method of the coal-based graphene are overcome, the resource utilization of the waste coal gangue is solved, the thought is provided for the research of the graphene, and the development and the utilization of downstream products of the waste coal gangue can be expanded. The preparation method is simple and easy to operate, harmful impurities in the waste coal gangue can be effectively removed, the prepared three-dimensional reticular graphene is good in quality and high in purity, can be selected in any required form, and can be customized according to market customer requirements, and the three-dimensional reticular graphene comprises a plurality of fields of pollutant adsorption, gas sensors, lithium ion batteries, supercapacitors, modified cement concrete and the like.
In order to achieve the above object, the present invention provides the following technical solutions.
A preparation process for preparing three-dimensional porous graphene with low cost specifically comprises the following steps:
step 1, selecting a residual coal source of the gangue from one or more of anthracite, bituminous coal, subbituminous coal and lignite.
And 2, mechanically crushing the selected coal gangue residual coal source.
And 3, separating organic components and mineral components from the crushed residual coal source by floatation.
And 4, grinding the separated organic component wet powder to 200-500 meshes.
Step 5, adding a catalyst and a nanoscale organic component, blending and grinding to obtain a uniform mixture, wherein the mass ratio of the catalyst to the organic component is 0.1-1:1.
and 6, treating the mixture at a high temperature of 2000-3000 ℃ for 1-24 hours, and charging high-purity nitrogen or high-purity argon shielding gas in the treatment process to graphitize the mixture.
And 7, blending 1 part by mass of graphitized organic components with 40-100 parts by mass of concentrated sulfuric acid and 6-9 parts by mass of concentrated phosphoric acid, stirring in an ice water bath to obtain a uniform mixed solution, adding 25-60 parts by mass of potassium permanganate, heating to 30-40 ℃, reacting for 90-150min, adding 50-120 parts by mass of deionized water, heating to 80-100 ℃ and reacting for 15-30min, adding 7-10 parts by mass of hydrogen peroxide, stirring to golden yellow, centrifugally washing, and then using ultrasonic shearing to crush to obtain the graphene oxide aqueous solution. And carrying out vacuum drying on the obtained graphene oxide aqueous solution, and sieving with a 500-mesh sieve to obtain graphene oxide powder.
And 8, after the obtained graphene oxide powder, the reducing agent and the deionized water are blended and stirred uniformly, placing the graphene oxide powder, the reducing agent and the deionized water in a polytetrafluoroethylene-lined high-pressure reaction kettle, controlling the reaction temperature to be 90-180 ℃ and the reaction time to be 3-8 hours, synthesizing the graphene oxide powder, and performing in-situ self-assembly under the pressure of water to obtain various three-dimensional porous graphene. Wherein the mass fraction of deionized water is 50-200 parts, and the mass ratio of graphene oxide to reducing agent is 1:0.5-3.
In the step 2, the mechanical crushing comprises one or more of ball milling, grinding and milling.
In the step 3, the floating separation of the powder components comprises using a liquid medium of alkane liquid, carbon tetrachloride, chloroform, ethers, esters, alkane, ethanol N-methylpyrrolidone, N-dimethylformamide and a combination thereof.
In the step 5, the catalyst comprises one or a combination of more of an iron-containing catalyst, a potassium-containing catalyst, an aluminum-containing catalyst, ferric oxide, nickel powder and iron powder.
In the step 8, the reducing agent is one or a combination of more of ascorbic acid, sodium bisulfate, sodium sulfide, hydrogen iodide and sodium iodide.
The preparation process for preparing the three-dimensional porous graphene at low cost mainly comprises carbon atoms, wherein the mass concentration of the prepared three-dimensional porous graphene is more than 95%, and the density is 3-15mg/cm 3 The adsorption capacity of the anionic dye is 1000-2000mg/g; the adsorption capacity to cations is generally 200-700mg/g.
The preparation process for preparing the three-dimensional porous graphene with low cost is characterized in that the prepared three-dimensional porous graphene and the derivative thereof are in the shape of sea urchin-like spheres with diameters of 50-100 nm; one of the columns has a diameter of 1.0-3.0cm and a height of 1-3 cm.
The preparation process for preparing the three-dimensional porous graphene with low cost can be used for modifying and modifying various materials; catalyst, resistance type gas sensor, lithium ion battery, supercapacitor, modified concrete field.
The preparation process for preparing the three-dimensional porous graphene with low cost can be used for preparing the three-dimensional porous graphene aqueous solution with surface modified biomacromolecules, proteins, nano metal particles and nano metal oxides (SnO) 2 、ZnO、Fe 2 O 3 、Fe 3 O 4 Etc.) and other carbon materials (carbon nanotubes, carbon quantum dots, etc.).
Compared with the prior art, the invention has the beneficial effects.
1. The selected carbon source takes the waste coal gangue as a basic raw material, so that the resource recycling of the waste coal gangue is realized, the material can be saved, the energy consumption is reduced, and the basic national policy of low carbon emission and sustainable development is realized.
2. The metal catalyst is added in the grinding process, so that the graphitization process is accelerated, the temperature of graphite is reduced, in addition, the graphitization degree is increased due to the metal catalyst in the graphitization process, the interlayer spacing is increased, intercalation is easier, and the quality of the peeled graphene is higher.
3. The graphene oxide aqueous solution is used as a precursor for in-situ self-assembly, so that stacking among graphene sheets is effectively reduced, and the excellent performance of graphene is effectively reserved. The three-dimensional porous graphene prepared by the method has more uniform distribution pore diameter and reduced average pore diameter, can be modified on the basis of the original requirements, and can effectively regulate and control the electrical, optical, chemical, mechanical and other characteristics of the graphene.
4. The preparation process is mild, no waste with environmental damage is generated, and meanwhile, the preparation process is simple and has lower requirements on machinery. The three-dimensional porous graphene with higher quality is prepared from a low-cost carbon source by adopting a low-cost preparation process, can be prepared in a large quantity, and is beneficial to the research and development of downstream products of the three-dimensional porous graphene: pollutant adsorption, resistance type gas sensors, lithium ion batteries, supercapacitors, modified cement concrete and other fields.
Drawings
FIG. 1 shows a three-dimensional porous graphene material prepared by the method.
FIG. 2 is a scanning electron microscope photograph of graphene oxide prepared according to the present invention.
FIG. 3 is a scanning electron microscope photograph of three-dimensional porous reticular graphene prepared by the method.
FIG. 4 the present invention is a heavy metal Pb 2+ Adsorption curve of (2).
Detailed Description
The present invention is described in detail below with reference to examples to facilitate understanding of the present invention by those skilled in the art. It is particularly pointed out herein that the examples are only intended to further illustrate the invention and are not to be construed as limiting the scope of the invention, since modifications and variations of the invention, which are not essential to the art, will be apparent to those skilled in the art from the foregoing description. Meanwhile, the raw materials mentioned below are not specified, and are all commercial products; the process steps or extraction methods not mentioned in detail are all those known to the person skilled in the art.
A preparation process for preparing three-dimensional porous graphene with low cost specifically comprises the following steps:
step 1, selecting a residual coal source of the gangue from one or more of anthracite, bituminous coal, subbituminous coal and lignite.
And 2, mechanically crushing the selected coal gangue residual coal source.
And 3, separating organic components and mineral components from the crushed residual coal source by floatation.
And 4, grinding the separated organic component wet powder to 200-500 meshes.
Step 5, adding a catalyst and a nanoscale organic component, blending and grinding to obtain a uniform mixture, wherein the mass ratio of the catalyst to the organic component is 0.1-1:1.
and 6, treating the mixture at a high temperature of 2000-3000 ℃ for 1-24 hours, and charging high-purity nitrogen or high-purity argon shielding gas in the treatment process to graphitize the mixture.
And 7, blending 1 part by mass of graphitized organic components with 40-100 parts by mass of concentrated sulfuric acid and 6-9 parts by mass of concentrated phosphoric acid, stirring in an ice water bath to obtain a uniform mixed solution, adding 25-60 parts by mass of potassium permanganate, heating to 30-40 ℃, reacting for 90-150min, adding 50-120 parts by mass of deionized water, heating to 80-100 ℃ and reacting for 15-30min, adding 7-10 parts by mass of hydrogen peroxide, stirring to golden yellow, centrifugally washing, and then using ultrasonic shearing to crush to obtain the graphene oxide aqueous solution. And carrying out vacuum drying on the obtained graphene oxide aqueous solution, and sieving with a 500-mesh sieve to obtain graphene oxide powder.
And 8, after uniformly blending and stirring the obtained graphene oxide powder, a reducing agent and deionized water, placing the graphene oxide powder in a polytetrafluoroethylene-lined autoclave, controlling the reaction temperature to be 90-180 ℃ and the reaction time to be 3-8 hours, synthesizing the graphene oxide powder under the pressure of water, and performing in-situ self-assembly to obtain various three-dimensional porous graphene. Wherein the mass fraction of deionized water is 50-200 parts, and the mass ratio of graphene oxide to reducing agent is 1:0.5-3.
In the step 2, the mechanical crushing comprises one or more of ball milling, grinding and milling.
In the step 3, the floating separation of the powder components comprises using a liquid medium of alkane liquid, carbon tetrachloride, chloroform, ethers, esters, alkane, ethanol N-methylpyrrolidone, N-dimethylformamide and a combination thereof.
In the step 5, the catalyst comprises one or a combination of more of an iron-containing catalyst, a potassium-containing catalyst, an aluminum-containing catalyst, ferric oxide, nickel powder and iron powder.
In the step 8, the reducing agent is one or a combination of more of ascorbic acid, sodium bisulfate, sodium sulfide, hydrogen iodide and sodium iodide.
The preparation process for preparing the three-dimensional porous graphene at low cost mainly comprises carbon atoms, wherein the mass concentration of the prepared three-dimensional porous graphene is more than 95%, and the density is 3-15mg/cm 3 For anionsThe adsorption capacity of the dye is 1000-2000mg/g; the adsorption capacity to cations is generally 200-700mg/g.
The preparation process for preparing the three-dimensional porous graphene with low cost is characterized in that the prepared three-dimensional porous graphene and the derivative thereof are in the shape of sea urchin-like spheres with diameters of 50-100 nm; one of the columns has a diameter of 1.0-3.0cm and a height of 1-3 cm.
The preparation process for preparing the three-dimensional porous graphene with low cost can be used for modifying and modifying various materials; catalyst, resistance type gas sensor, lithium ion battery, supercapacitor, modified concrete field.
The preparation process for preparing the three-dimensional porous graphene with low cost can be used for preparing the three-dimensional porous graphene aqueous solution with surface modified biomacromolecules, proteins, nano metal particles and nano metal oxides (SnO) 2 ，ZnO，Fe 2 O 3 、Fe 3 O 4 Etc.) and other carbon materials (carbon nanotubes, carbon quantum dots, etc.).
Example 1.
Taking residues of anthracite, mechanically crushing, using carbon tetrachloride to float out organic components and mineral components, carrying out wet powder grinding on the obtained organic components to 500 meshes on the obtained organic components under the premise of not adding a catalyst, and mixing the obtained organic components with iron powder to obtain a mixture of 1: the mass ratio of 0.1 is evenly mixed by ball milling. Then placing the mixture in a graphitization furnace at 2000 ℃ for 9 hours. Taking 1g of graphitized material and 40g of concentrated sulfuric acid, 6g of concentrated phosphoric acid, stirring uniformly under the condition of ice water bath stirring, then adding 30g of potassium permanganate, and reacting for 90min at the temperature of 30 ℃. And adding 50g of deionized water, continuously reacting for 15min at 90 ℃, adding 7g of hydrogen peroxide, stirring uniformly to golden yellow, centrifugally washing, and performing ultrasonic shearing and crushing to obtain uniform graphene oxide suspension. And (3) drying the obtained graphene oxide solution for 24 hours in vacuum, and sieving with a 500-mesh sieve to obtain graphene oxide powder. Adding 0.15g of graphene oxide powder and 0.15g of ascorbic acid into 50mL of deionized water, placing into a polytetrafluoroethylene-lined reaction kettle, performing reaction treatment at 100 ℃ for 6 hours, and performing freeze drying for 24 hours to obtain the three-dimensional porous graphene.
Example 2.
Mechanically crushing residues in the bituminous coal, then, floating out organic components and mineral components by using chloroform, carrying out wet powder grinding on the obtained organic components to 500 meshes on the premise of not adding a catalyst, and mixing the wet powder with ferric oxide in a ratio of 1: the mass ratio of 0.1 is evenly mixed by ball milling. Then placing the mixture in a graphitization furnace at 2000 ℃ for 9 hours. Taking 1g of graphitized material and 50g of concentrated sulfuric acid, 8g of concentrated phosphoric acid, stirring uniformly under the condition of ice water bath stirring, then adding 40g of potassium permanganate, and reacting for 90min at 40 ℃. And adding 50g of deionized water, continuously reacting for 15min at 90 ℃, adding 9g of hydrogen peroxide, stirring uniformly to golden yellow, centrifugally washing, and performing ultrasonic shearing and crushing to obtain a uniform graphene oxide solution. And (3) vacuum drying the obtained graphene oxide for 24 hours, and sieving the graphene oxide with a 500-mesh sieve to obtain graphene oxide powder. Weighing 0.3g of graphene oxide powder, blending 0.45g of ascorbic acid with 100ml of deionized water, loading into a polytetrafluoroethylene lining reaction kettle, reacting for 4 hours at 100 ℃, and freeze-drying for 48 hours to obtain the three-dimensional porous graphene.
Example 3.
Mechanically pulverizing residues in anthracite, separating out organic components and mineral components by using chloroform, carrying out wet powder grinding on the obtained organic components to 500 meshes under the premise of not adding a catalyst, and mixing with ferric oxide and ferric sulfate (ferric oxide and ferric sulfate are 1:1) in a ratio of 1: the mass ratio of 0.1 is evenly mixed by ball milling. Then placing the mixture in a graphitization furnace at 2000 ℃ for 6 hours. Taking 1g of graphitized material and 50g of concentrated sulfuric acid, 8g of concentrated phosphoric acid, stirring uniformly under the condition of ice water bath stirring, then adding 40g of potassium permanganate, and reacting for 90min at 40 ℃. And adding 50g of deionized water, continuously reacting for 15min at 90 ℃, adding 10g of hydrogen peroxide, stirring uniformly to golden yellow, centrifuging, and performing ultrasonic shearing and crushing to obtain uniform graphene oxide suspension. And (3) drying the obtained graphene oxide solution for 24 hours in vacuum, and sieving with a 500-mesh sieve to obtain graphene oxide powder. Weighing 0.04g of graphene oxide powder, 0.08g of hydrogen iodide, mixing with 100ml of deionized water, loading into a polytetrafluoroethylene-lined reaction kettle, reacting for 4 hours at 100 ℃, and freeze-drying for 48 hours to obtain the three-dimensional porous graphene.
Fig. 1 shows that the prepared three-dimensional graphene has a porous structure, which is beneficial for combination with other substances.
Fig. 2 shows that the graphene oxide has a smooth surface, and the edge part of the material is in a wrinkled state and is in an irregular sheet shape.
From fig. 3, it can be seen that the three-dimensional graphene sheets are cross-linked with each other, have a flower-like structure, are wrapped more densely, and can fully exert the excellent characteristics of the three-dimensional graphene sheets as energy storage or adsorption.
Investigation of Pb at different concentrations Using an ultraviolet Spectrophotometer 2+ The adsorption rate at the concentration, as apparent from FIG. 4, shows the prepared p-Pb 2+ Is effective, especially at 80mg/mL Pb 2+ The adsorption rate is as high as 94% under the concentration. The reason is that the three-dimensional graphene is used as the adsorbent, the larger specific surface area of the three-dimensional graphene provides larger adsorption points, and in addition, the adsorption effect of the compact flower-like structure on cations is remarkably improved.
Claims (6)
1. A preparation process for preparing three-dimensional porous graphene at low cost comprises the following preparation steps:
step 1, selecting a residual coal source of coal gangue from one or more combinations of anthracite, bituminous coal, subbituminous coal and lignite;
step 2, mechanically crushing the selected coal gangue residual coal source;
step 3, floating and separating organic components and mineral components from crushed residual coal sources, wherein floating and settling separation of the powder components comprises using one or two liquid media of carbon tetrachloride and chloroform;
step 4, ball milling the separated organic component wet powder to 200-500 meshes;
step 5, adding a catalyst and a nanoscale organic component, blending and grinding to obtain a uniform mixture, wherein the mass ratio of the catalyst to the organic component is 0.1-1:1, a step of;
step 6, treating the mixture at a high temperature of 2000-3000 ℃ for 1-24 hours, and charging high-purity nitrogen or high-purity argon shielding gas in the treatment process to graphitize the mixture;
step 7, blending 1 part by mass of graphitized organic components with 40-100 parts by mass of concentrated sulfuric acid and 6-9 parts by mass of concentrated phosphoric acid, stirring in an ice water bath to obtain a uniform mixed solution, adding 25-60 parts by mass of potassium permanganate, heating to 30-40 ℃, reacting for 90-150min, then adding 50-120 parts by mass of deionized water, heating to 80-100 ℃ for reacting for 15-30min, adding 7-10 parts by mass of hydrogen peroxide, stirring to golden yellow, centrifugally washing, using ultrasonic shearing and crushing to obtain graphene oxide aqueous solution, and vacuum drying the obtained graphene oxide aqueous solution, and sieving with a 500-mesh sieve to obtain graphene oxide powder;
step 8, after the obtained graphene oxide powder, a reducing agent and deionized water are mixed and stirred uniformly, placing the graphene oxide powder, the reducing agent and deionized water in a polytetrafluoroethylene-lined reaction kettle, controlling the reaction temperature to be 100-180 ℃ and the reaction time to be 3-8 hours, synthesizing the graphene oxide powder under the pressure of water, and performing in-situ self-assembly to obtain various three-dimensional porous graphene; the prepared three-dimensional porous graphene mainly comprises carbon atoms, the mass concentration of the three-dimensional porous graphene exceeds 95%, and the density of the three-dimensional porous graphene is 3-15mg/cm 3 The adsorption capacity of the anionic dye is 1000-2000mg/g; the adsorption capacity to cations is 200-700mg/g; the prepared three-dimensional porous graphene is in a sea urchin-shaped spherical shape with the diameter of 50-100 nm;
the reducing agent is one or more of ascorbic acid, sodium bisulfate, sodium sulfide, hydrogen iodide and sodium iodide.
2. The process for preparing three-dimensional porous graphene at low cost according to claim 1, wherein in the step 2, mechanical crushing comprises one or more of ball milling, grinding and milling.
3. The process for preparing three-dimensional porous graphene at low cost according to claim 1, wherein in the step 5, the catalyst comprises one or more of an iron-containing catalyst, a potassium-containing catalyst, an aluminum-containing catalyst, and nickel powder.
4. The preparation process for preparing three-dimensional porous graphene with low cost according to claim 1, wherein in the step 8, the mass fraction of deionized water is 50-200 parts, and the mass ratio of graphene oxide to reducing agent is 1:0.5-3.
5. The preparation process for preparing the three-dimensional porous graphene with low cost according to claim 1, wherein the prepared three-dimensional porous graphene can be used for modification and modification of various materials; catalyst, resistance type gas sensor, lithium ion battery, supercapacitor, modified concrete field.
6. The process for preparing three-dimensional porous graphene with low cost according to claim 1, wherein the prepared three-dimensional porous graphene aqueous solution can be used for surface modification of biological macromolecules, proteins, nano metal particles, nano metal oxides and other carbon materials.
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