CN111547709A - Biomass three-dimensional porous graphene and preparation method thereof - Google Patents
Biomass three-dimensional porous graphene and preparation method thereof Download PDFInfo
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- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
- C01B32/182—Graphene
- C01B32/184—Preparation
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- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/20—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising free carbon; comprising carbon obtained by carbonising processes
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Abstract
The invention discloses biomass three-dimensional porous graphene and a preparation method thereof, and the preparation method comprises the following steps: uniformly mixing biomass powder and inorganic salt, carrying out pyrolysis reaction under the protection of inert gas, then cooling to room temperature, washing away an inorganic salt template by using hot water at 90-100 ℃, filtering, washing and recovering molten salt, and drying an obtained black solid product to obtain the biomass three-dimensional graphene. According to the invention, the biomass material and the water-soluble inorganic salt are used for preparing the three-dimensional porous graphene, and the fused salt is used for catalyzing the biomass cracking, so that the method has the characteristic of short time for high-temperature cracking; nanometer or micron salt particles formed by recrystallization of the molten salt in the cooling stage are used as templates and pore-forming agents for carbon precipitation embedded in the molten salt, three-dimensional graphene with high specific surface area is precipitated on the surface of the salt particles, the preparation process is simple and easy to implement, the preparation period of the three-dimensional graphene can be shortened, and the method is more environment-friendly than a method for preparing the graphene by an oxidation-reduction method.
Description
Technical Field
The invention relates to the technical field of graphene preparation, and particularly relates to biomass three-dimensional porous graphene and a preparation method thereof.
Background
Since two scientists of Manchester university in England Andelim Geim (Andre Geim) and Constantin Novoselov (Konstantin Novoselov) prepared graphene by a mechanical stripping method (Science,2004,306, 666) and gained Nobel prize in 2010, graphene is favored by researchers due to its excellent electrical conductivity and mechanical properties and ultrahigh thermal conductivity at room temperature, and has important application prospects in the aspects of materials Science, micro-nano processing, energy, sensors, drug delivery and the like, and is considered to be a revolutionary material in the future.
At present, the main methods for preparing graphene comprise a mechanical stripping method, a redox method, a silicon carbide epitaxial method, a chemical vapor deposition method and the like, but the methods are difficult to realize batch production due to complex preparation process, long preparation period, high production cost or environmental pollution. Therefore, in order to overcome the problems in the prior art, it is necessary to develop a green and efficient preparation method of three-dimensional graphene with a high specific surface area, which is environment-friendly, simple in preparation process, low in price and easy to popularize on a large scale.
Disclosure of Invention
Aiming at the defects in the prior art, the invention provides biomass three-dimensional porous graphene and a preparation method thereof.
In order to achieve the purpose, the invention adopts the following technical scheme:
the preparation method of the biomass three-dimensional porous graphene comprises the following steps:
(1) drying and crushing the biomass material to obtain biomass powder for later use;
(2) grinding and uniformly mixing the biomass powder obtained in the step (1) and water-soluble inorganic salt according to the mass ratio of 1:4-10, carrying out pyrolysis reaction in an inert gas atmosphere, and then cooling to room temperature;
(3) washing the inorganic salt template by using hot water of 90-100 ℃, filtering, washing and recovering molten salt, and drying the obtained black solid product to obtain the biomass three-dimensional graphene.
Furthermore, the biomass material comprises agriculture and forestry resources and wastes, and the agriculture and forestry resources and wastes comprise at least one of rice hulls, corncobs, corn straws, peanut shells, walnut shells and sawdust. The sawdust includes but is not limited to sawdust of bamboo, pine, birch, fir, redwood, eucalyptus, poplar, willow, elm, mahogany, oak and rattan.
Further, the water-soluble inorganic salt is at least one of a water-soluble chloride salt and a water-soluble carbonate salt.
Further, the water-soluble chlorine salt is at least one of NaCl and KCl.
Further, the water-soluble carbonate is Na2CO3、K2CO3At least one of (1).
Specifically, the mass ratio of the biomass powder to the water-soluble inorganic salt is 1:4-10, including 1:4, 1:4.5, 1:5, 1:5.5, 1:6, 1:6.5, 1:7, 1:7.5, 1:8, 1:8.5, 1:9, 1:9.5, 1:10 and the ratio of the foregoing ratios.
Further, the biomass material drying conditions in (1) are as follows: drying for 8-16h at the temperature of 100 ℃ and 130 ℃.
Further, the particle size of the biomass powder is 60 mesh or less.
Further, the conditions for carrying out the pyrolysis reaction in (2) are as follows: heating from room temperature to 550-1000 deg.C at 5-30 deg.C/min, and maintaining for 10-60 min. The method adopts a carbon dissolution precipitation mechanism with molten salt particles as a template, nanometer and/or micrometer salt particles formed by recrystallization of the molten salt in a cooling stage are used as a template and a pore-forming agent for carbon precipitation embedded in the molten salt, three-dimensional graphene with high specific surface area is precipitated on the surface of the salt particles, and the reaction product is obtained by washing an inorganic salt template with water to recover the molten salt.
Further, the inert gas in (2) is at least one of nitrogen, argon or helium.
The invention also provides the three-dimensional porous graphene prepared by the preparation method of the biomass three-dimensional porous graphene.
The invention also provides application of the three-dimensional porous graphene in the fields of preparation of super capacitors, sensors, catalysis, fuel cells, adsorbents and lithium-air batteries.
The invention has the beneficial effects that:
(1) according to the invention, the biomass material and the water-soluble inorganic salt are used for preparing the three-dimensional porous graphene, and the fused salt is used for catalyzing the biomass cracking, so that the method has the characteristic of short time for high-temperature cracking; nanometer or micron salt particles formed by recrystallization of the molten salt in the cooling stage are used as templates and pore-forming agents for carbon precipitation embedded in the molten salt, three-dimensional graphene with high specific surface area is precipitated on the surface of the salt particles, the preparation process is simple and easy to implement, and the preparation period of the three-dimensional graphene can be shortened;
(2) according to the method, the water-soluble salt is used as the molten salt, the biomass with low price is used as the carbon source, the water-soluble salt can be recycled in the preparation process, the production cost of the three-dimensional graphene is reduced, and the possibility is provided for large-scale production of the graphene.
Drawings
In order to more clearly illustrate the detailed description of the invention or the technical solutions in the prior art, the drawings that are needed in the detailed description of the invention or the prior art will be briefly described below. Throughout the drawings, like elements or portions are generally identified by like reference numerals. In the drawings, elements or portions are not necessarily drawn to scale.
Fig. 1 is an SEM image of three-dimensional graphene prepared in example 1 of the present invention;
fig. 2 is an SEM image of three-dimensional graphene prepared in example 2 of the present invention;
fig. 3 is an SEM image of three-dimensional graphene prepared in example 3 of the present invention;
fig. 4 is an SEM image of three-dimensional graphene prepared in example 4 of the present invention;
fig. 5 is an SEM image of three-dimensional graphene prepared in example 5 of the present invention;
fig. 6 is an SEM image of three-dimensional graphene prepared in example 6 of the present invention;
fig. 7 is an SEM image of three-dimensional graphene prepared in example 7 of the present invention;
fig. 8 is an SEM image of three-dimensional graphene prepared in example 8 of the present invention;
fig. 9 is an SEM image of three-dimensional graphene prepared in example 9 of the present invention;
fig. 10 is an SEM image of three-dimensional graphene prepared in example 10 of the present invention.
Detailed Description
Embodiments of the present invention will be described in detail below with reference to the accompanying drawings. The following examples are only for illustrating the technical solutions of the present invention more clearly, and therefore are only examples, and the protection scope of the present invention is not limited thereby.
It is to be noted that, unless otherwise specified, technical or scientific terms used herein shall have the ordinary meaning as understood by those skilled in the art to which the invention pertains.
The experimental procedures in the following examples are conventional unless otherwise specified. The test materials used in the following examples were purchased from a conventional biochemical reagent store unless otherwise specified. In the quantitative tests in the following examples, three replicates were set, and the data are the mean or the mean ± standard deviation of the three replicates.
The invention provides a preparation method of biomass three-dimensional porous graphene, which comprises the following steps:
(1) drying and crushing the biomass material to obtain biomass powder for later use;
(2) grinding and uniformly mixing the biomass powder obtained in the step (1) and water-soluble inorganic salt according to the mass ratio of 1:4-10, carrying out pyrolysis reaction in an inert gas atmosphere, and then cooling to room temperature;
(3) washing the inorganic salt template by using hot water of 90-100 ℃, filtering, washing and recovering molten salt, and drying the obtained black solid product to obtain the biomass three-dimensional graphene.
The biomass material comprises agriculture and forestry resources and wastes, and the agriculture and forestry resources and wastes comprise at least one of rice hulls, corncobs, corn straws, peanut shells, walnut shells and sawdust. The sawdust includes but is not limited to sawdust of bamboo, pine, birch, fir, redwood, eucalyptus, poplar, willow, elm, mahogany, oak and rattan.
Specifically, the water-soluble inorganic salt is at least one of a water-soluble chloride salt and a water-soluble carbonate salt.
Specifically, the water-soluble chlorine salt is at least one of NaCl and KCl.
Specifically, the water-soluble carbonate is Na2CO3、K2CO3At least one of (1).
The invention will now be described with reference to specific embodiments.
Example 1
Oven drying corn cob at 120 deg.C for 12 hr, pulverizing to 60 mesh below with pulverizer to obtain corn cob powder, and mixing corn cob powder 1.0g and Na 5.0g2CO3Mixing, grinding, placing in corundum crucible, placing in tubular atmosphere furnace under the protection of Ar gas to obtain the invented productAnd (3) heating to 900 ℃ from room temperature at the temperature of 5 ℃/min, keeping the temperature of 900 ℃ for 10min, then cooling to room temperature, washing off the inorganic salt template by using hot water (90-100 ℃), filtering, washing and recovering molten salt, and drying the obtained black solid product to obtain the biomass three-dimensional graphene. This example uses Na2CO3The structure of the three-dimensional graphene prepared by using molten salt and corncobs as carbon sources is shown in figure 1.
Example 2
Oven drying corn cob at 120 deg.C for 12 hr, pulverizing to below 60 mesh with pulverizer to obtain corn cob powder, mixing 1.0g corn cob powder and 5.0g K2CO3Uniformly mixing and grinding, placing in a corundum crucible, placing in a tubular atmosphere furnace, raising the temperature from room temperature to 900 ℃ at the speed of 5 ℃/min under the protection of Ar gas, keeping the temperature at 900 ℃ for 10min, then cooling to room temperature, washing off an inorganic salt template by using hot water (90-100 ℃), filtering, washing and recovering molten salt, and simultaneously drying the obtained black solid product to obtain the biomass three-dimensional graphene as shown in figure 2.
Example 3
Oven drying corn cob at 120 deg.C for 12 hr, pulverizing to 60 mesh or less with pulverizer to obtain corn cob powder, mixing with 2.5g Na2CO3And 2.5g K2CO3Uniformly mixing and grinding the mixture, uniformly mixing the mixture with 1.0g of corncob powder, placing the mixture in a corundum crucible, placing the corundum crucible in a tubular atmosphere furnace, heating the mixture from room temperature to 900 ℃ at the speed of 5 ℃/min under the protection of Ar gas, keeping the temperature of the mixture constant at 900 ℃ for 10min, then cooling the mixture to room temperature, washing an inorganic salt template by hot water (90-100 ℃), filtering, washing and recovering molten salt, and simultaneously drying the obtained black solid product to obtain the biomass three-dimensional graphene as shown in figure 3.
Example 4
Drying corncobs at 120 ℃ for 12h, crushing the corncobs to be below 60 meshes by using a crusher to obtain corncob powder, uniformly grinding 5.0g of NaCl, uniformly mixing the ground corncob powder with 1.0g of corncob powder, placing the mixture in a corundum crucible, placing the corundum crucible in a tubular atmosphere furnace, raising the temperature from room temperature to 900 ℃ at the speed of 5 ℃/min under the protection of Ar gas, keeping the temperature of the furnace at 900 ℃ for 10min, then cooling the furnace to the room temperature, washing off an inorganic salt template by using hot water (90-100 ℃), filtering, washing and recovering molten salt, and drying the obtained black solid product to obtain the biomass three-dimensional graphene, wherein the biomass three-dimensional graphene is shown in figure 4. The product graphene is less in generation amount and mainly distributed on the surface.
Example 5
Drying corncobs at 120 ℃ for 12h, crushing the corncobs to be below 60 meshes by using a crusher to obtain corncob powder, uniformly grinding 5.0g of KCl, uniformly mixing the ground corncob powder with 1.0g of corncob powder, placing the mixture in a corundum crucible, placing the mixture in a tubular atmosphere furnace, heating the mixture from room temperature to 900 ℃ at the speed of 5 ℃/min under the protection of Ar gas, keeping the temperature of the mixture at 900 ℃ for 10min, then cooling the mixture to room temperature, washing off an inorganic salt template by using hot water (90-100 ℃), filtering, washing and recovering molten salt, and drying the obtained black solid product to obtain the biomass three-dimensional graphene, wherein the biomass three-dimensional graphene is shown in figure 5.
Example 6
Drying corncobs at 120 ℃ for 12h, crushing the corncobs to be below 60 meshes by using a crusher to obtain corncob powder, mixing and grinding 2.5g of NaCl and 2.5g of KCl uniformly, mixing the ground corncob powder with 1.0g of corncob powder uniformly, placing the mixture in a corundum crucible, placing the corundum crucible in a tubular atmosphere furnace, heating the mixture from room temperature to 900 ℃ at the speed of 5 ℃/min under the protection of Ar gas, keeping the temperature of the mixture at 900 ℃ for 10min, then cooling the mixture to room temperature, washing off an inorganic salt template by using hot water (90-100 ℃), filtering, washing and recovering molten salt, and drying the obtained black solid product to obtain the biomass three-dimensional graphene as shown in figure 6.
Example 7
Oven drying peanut shell at 120 deg.C for 12 hr, pulverizing to 60 mesh or less with pulverizer to obtain peanut shell powder, adding 5.0g Na2CO3Uniformly grinding, uniformly mixing with 1.0g of peanut shell powder, placing in a corundum crucible, placing in a tubular atmosphere furnace, heating to 900 ℃ from room temperature at the speed of 5 ℃/min under the protection of Ar gas, keeping the temperature of 900 ℃ for 10min, then cooling to room temperature, washing off an inorganic salt template by hot water (90-100 ℃), filtering, washing and recovering molten salt, and simultaneously drying the obtained black solid product to obtain the biomass three-dimensional graphene as shown in figure 7.
Example 8
Drying peanut shell at 120 deg.C for 12 hr, and pulverizing with pulverizerSieving with 60 mesh sieve to obtain peanut shell powder, and mixing with 5.0gK2CO3Uniformly grinding, uniformly mixing with 1.0g of peanut shell powder, placing in a corundum crucible, placing in a tubular atmosphere furnace, heating to 900 ℃ from room temperature at the speed of 5 ℃/min under the protection of Ar gas, keeping the temperature of 900 ℃ for 10min, then cooling to room temperature, washing off an inorganic salt template by hot water (90-100 ℃), filtering, washing and recovering molten salt, and simultaneously drying the obtained black solid product to obtain the biomass three-dimensional graphene as shown in figure 8.
Example 9
Oven drying peanut shell at 120 deg.C for 12 hr, pulverizing to 60 mesh or less with pulverizer to obtain peanut shell powder, and mixing with 2.5g Na2CO3And 2.5g K2CO3Uniformly mixing and grinding, uniformly mixing with 1.0g of peanut shell powder, placing in a corundum crucible, placing in a tubular atmosphere furnace, heating to 900 ℃ from room temperature at the speed of 5 ℃/min under the protection of Ar gas, keeping the temperature of 900 ℃ for 10min, then cooling to room temperature, recovering molten salt by using hot water (90-100 ℃), filtering, washing and recovering the molten salt, and simultaneously drying the obtained black solid product to obtain the biomass three-dimensional graphene as shown in figure 9.
Example 10
Drying peanut shells at 120 ℃ for 12h, crushing the peanut shells to be below 60 meshes by using a crusher to obtain peanut shell powder, mixing and grinding 2.5g of NaCl and 2.5g of KCl uniformly, mixing the ground peanut shell powder uniformly with 1.0g of peanut shell powder, placing the mixture in a corundum crucible, placing the corundum crucible in a tubular atmosphere furnace, heating the mixture from room temperature to 900 ℃ at the speed of 5 ℃/min under the protection of Ar gas, keeping the temperature of the mixture at 900 ℃ for 10min, then cooling the mixture to room temperature, washing off an inorganic salt template by using hot water (90-100 ℃), filtering, washing and recovering molten salt, and drying the obtained black solid product to obtain the biomass three-dimensional graphene, wherein the biomass three-dimensional graphene is shown in figure 10.
The above examples are preferred embodiments of the present invention, but the embodiments of the present invention are not limited to the above examples, and the biomass material may be a mixture of any two or more of peanut shell and corn cob, other biological materials, etc.; the ratio of the biological material to the molten salt is not limited to 1: 4-10; the inert gas can also be nitrogen, argon or heliumMeaning a mixture of more than two, etc. The reaction temperature is not limited to 900 ℃, the heat treatment is not limited to 10min, and the molten salt is not limited to NaCl, KCl and Na2CO3、K2CO3Any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the invention are intended to be included within the scope of the invention.
Finally, it should be noted that: the above embodiments are only used to illustrate the technical solution of the present invention, and not to limit the same; while the invention has been described in detail and with reference to the foregoing embodiments, it will be understood by those skilled in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some or all of the technical features may be equivalently replaced; such modifications and substitutions do not depart from the spirit and scope of the present invention, and they should be construed as being included in the following claims and description.
Claims (9)
1. The preparation method of the biomass three-dimensional porous graphene is characterized by comprising the following steps:
(1) drying and crushing the biomass material to obtain biomass powder for later use;
(2) grinding and uniformly mixing the biomass powder obtained in the step (1) and water-soluble inorganic salt according to the mass ratio of 1:4-10, carrying out pyrolysis reaction in an inert gas atmosphere, and then cooling to room temperature;
(3) washing the inorganic salt template by using hot water of 90-100 ℃, filtering, washing and recovering molten salt, and drying the obtained black solid product to obtain the biomass three-dimensional graphene.
2. The method for preparing the biomass three-dimensional porous graphene according to claim 1, wherein the biomass material comprises agriculture and forestry resources and wastes, including at least one of rice hulls, corn cobs, corn stalks, peanut shells, walnut shells and sawdust.
3. The method for preparing the biomass three-dimensional porous graphene according to claim 1, wherein the water-soluble inorganic salt is at least one of a water-soluble chloride salt and a water-soluble carbonate salt.
4. The method for preparing the biomass three-dimensional porous graphene according to claim 3, wherein the water-soluble chloride salt is at least one of NaCl and KCl; the water-soluble carbonate is Na2CO3、K2CO3At least one of (1).
5. The method for preparing biomass three-dimensional porous graphene according to claim 1, wherein the biomass material in (1) is dried under the following conditions: drying for 8-16h at the temperature of 100 ℃ and 130 ℃; the particle size of the biomass powder is below 60 meshes.
6. The method for preparing biomass three-dimensional porous graphene according to claim 1, wherein the conditions for performing the pyrolysis reaction in (2) are as follows: heating from room temperature to 550-1000 deg.C at 5-30 deg.C/min, and maintaining for 10-60 min.
7. The method for preparing biomass three-dimensional porous graphene according to claim 1, wherein the inert gas in (2) is at least one of nitrogen, argon or helium.
8. The three-dimensional porous graphene prepared by the preparation method of biomass three-dimensional porous graphene according to any one of claims 1 to 7.
9. The three-dimensional porous graphene according to claim 8, wherein the three-dimensional porous graphene is applied to the fields of preparation of supercapacitors, sensors, catalysis, fuel cells, adsorbents and lithium-air batteries.
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| CN113307254A (en) * | 2021-06-24 | 2021-08-27 | 武汉科技大学 | Method for preparing three-dimensional porous graphene sheet by using low-temperature double-salt compound and application |
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| CN114180560A (en) * | 2021-12-21 | 2022-03-15 | 山西大学 | Preparation method of coal-based graphene in molten salt system |
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| CN114180560A (en) * | 2021-12-21 | 2022-03-15 | 山西大学 | Preparation method of coal-based graphene in molten salt system |
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