CN114620717A - Preparation method of ordered double-mesoporous carbon graphene material or ordered double-mesoporous carbon material - Google Patents
Preparation method of ordered double-mesoporous carbon graphene material or ordered double-mesoporous carbon material Download PDFInfo
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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
- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
- C01B32/182—Graphene
- C01B32/184—Preparation
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/20—Graphite
- C01B32/205—Preparation
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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
- C01B2204/04—Specific amount of layers or specific thickness
-
- 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
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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 relates to a preparation method of an ordered double-mesoporous carbon graphene material or an ordered double-mesoporous carbon material. Removing the nanocrystalline particle template by acid etching by using the carbon-coated binary superlattice as a template to obtain the double mesoporous carbon with a highly ordered structure; on the basis, the ordered double mesoporous graphene material is prepared by combining graphitization treatment. The novel double mesoporous carbon material can be prepared by regulating binary super crystals with different topological structures and controlling the reaction temperature of ligand crosslinking-carbonization, and the topological structures of the novel double mesoporous carbon material comprise NaCl, CsCl, CuAu and AlB2、MgZn2、CuAu3、FeC4、CaCu5、CaB6、NaZn13And (4) molding. The ordered double-mesoporous carbon material with the specific topological structure has good conductivity, has the characteristics of the ordered double-mesoporous material, shows ultrahigh specific surface area, pore volume and excellent mass transfer characteristic, and can be widely applied to energy storage devices such as double-layer capacitors, lithium ion batteries and the like.
Description
Technical Field
The invention belongs to the field of a carbon material preparation process, and particularly relates to a preparation method of an ordered double-mesoporous carbon graphene material or an ordered double-mesoporous carbon material. The ordered double mesoporous graphene prepared by the invention has the advantages of high specific surface area, excellent mass transfer characteristic and excellent conductivity of the ordered mesoporous material, and can be widely applied to energy storage materials.
Background
Nanoporous carbon materials are widely used in the fields of sensing devices, bioreactors, energy storage and conversion, etc. The three-dimensional ordered nano porous graphene superstructure combines the conductive advantages of graphene with the advantages of high specific surface area and mass transfer of a porous structure, and has great potential application value. At present, researchers have proposed many methods for synthesizing porous structures, such as zeolite templating methods, block copolymer soft templating methods, and the like. Due to the characteristics of the template, the method at the present stage cannot effectively realize the efficient preparation of ordered mesoporous carbon or graphene with specific pore size.
The binary superlattice is a solid material with a specific ordered structure, nanoparticles can maintain a stable ordered structure and can be selectively etched and removed, and organic molecular ligands on the surface can perform cross-linking-carbonization behaviors under certain conditions to form a three-dimensional through carbon skeleton. However, the current methods for the large-scale preparation of binary nanocrystals and in-situ ligand carbonization are not mature, and the phase purity of binary nanocrystals is not high. Therefore, the development of a proper method for preparing the ordered double mesoporous carbon material with the topological structure has important significance.
Disclosure of Invention
The invention aims to provide a preparation method of an ordered double-mesoporous carbon graphene material or an ordered double-mesoporous carbon material. The ordered double-mesoporous graphene obtained by the invention has rich and adjustable multi-level pore stacking structures, and has excellent conductivity of graphene and ultrahigh specific surface area of multi-level pores. The specific technical scheme is as follows:
the invention provides a preparation method of an ordered double-mesoporous carbon graphene material or an ordered double-mesoporous carbon material, which comprises the following steps:
(1) taking monodisperse colloid nano-particles with different sizes as an assembly unit, combining two kinds of nano-particles with effective particle diameter ratio, uniformly mixing the two kinds of nano-particles according to the chemical quantity ratio, and preparing a binary super-crystal by a co-assembly method;
(2) crosslinking and carbonizing the organic molecular ligand on the surface of the binary superlattice obtained in the step (1) by controlling the temperature of in-situ ligand carbonization;
(3) removing redundant nano particles on the surface of the product obtained in the step (2) by using acid solution etching to obtain an ordered double mesoporous carbon skeleton with a three-dimensional through structure;
(4) and (3) selecting a proper graphitization temperature, ensuring the stability of the ordered double-mesoporous framework obtained in the step (3), and simultaneously realizing graphitization of the carbon layer to obtain the ordered double-mesoporous graphene material or the ordered double-mesoporous carbon material with a topological structure.
In the invention, the monodisperse colloid nanoparticles in the step (1) have monodispersity and stability, the particle size is adjustable within 2-50 nm, the nanoparticles comprise inorganic nanoparticles which can be completely removed by an acid solution, organic molecular ligands such as oleic acid, oleylamine, mercaptan and oleoyl phosphoric acid are uniformly coated on the surfaces of the nanoparticles, the surfaces of the nanoparticles are exchanged into any molecular ligand through ligand exchange, and the nanoparticles can be placed in a solvent (n-hexane, chloroform, toluene, cyclohexane and the like) for a long time to keep colloid stability and no precipitation.
In the present invention, the ratio of the effective particle diameters of the two types of nanoparticles in the step (1) is the effective particle diameter (R) of the nanoparticleeff) Can be regarded as the sum of the radius of the core (R) and the length of the ligand (L), i.e.Reff= R + L; binary nanocrystals require the use of effective particlesThe preparation of the nano-particle combination with the diameter ratio of 0.35-0.85 can be realized by using the nano-particle combination comprising NaCl, CsCl, CuAu and AlB2、MgZn2、CuAu3、FeC4、CaCu5、CaB6Or NaZn13And any two-dimensional superlattice structure.
In the invention, the crosslinking temperature in the step (2) is 300-400 ℃, the carbonization temperature is 400-520 ℃, the heating rate is kept at 0.5-10 ℃ per minute, and the constant temperature time of crosslinking and carbonization is 60-180 minutes.
In the invention, the concentration of the acid solution in the step (3) is 1-6 mol/L, and the etching needs to be continuously carried out for a plurality of times, so that the etching is ensured to be carried out for more than 3 times.
In the invention, the graphitization temperature in the step (4) is more than 900 ℃, the heating rate is kept at 0.5-10 ℃ per minute, and the constant temperature time is kept at 60-180 minutes.
According to the invention, the ordered double-mesoporous graphene material obtained in the step (4) is composed of large and small mesopores with the size of 2-50 nm, the large and small mesopores are mutually communicated according to a certain accumulation mode to form a graphene framework, and the pore wall is composed of 3-6 layers of graphene.
In the invention, micropores are formed in the stacking gaps and the pore walls of the large and small mesopores in the ordered double-mesoporous graphene or the double-mesoporous carbon obtained in the step (4).
Compared with the existing preparation method of mesoporous carbon or graphene, the ordered double mesoporous carbon and graphene material prepared by the invention has the beneficial effects that:
(1) the method utilizes the binary nanocrystal superlattice as a template, adjusts the sizes of two mesopores according to the size of nanoparticles in the binary superlattice, and utilizes a nanoparticle stacking method to adjust the topological structure of the ordered double-mesopore graphene. The method is not reported, and is different from the traditional hard template method and the micelle liquid crystal method for preparing the prepared single mesoporous material.
(2) The topological structures of the ordered double-mesoporous carbon and graphene materials prepared by the method are adjustable, and all the ordered double-mesoporous structures comprise NaCl, CsCl, CuAu and AlB2、MgZn2、CuAu3、FeC4、CaCu5、CaB6、NaZn13The types and the like are prepared and reported for the first time, and the conventional synthetic method cannot be realized.
(3) According to the invention, organic ligand micromolecules inherent on the surface of the nanoparticle are converted into a carbon skeleton through the cross-linking-carbonizing technology of the in-situ ligand, a molecular pouring process needing additional addition of carbon source molecules is not involved, and a uniform and ultrathin carbon layer/graphene layer (3-6 layers of graphene) can be formed.
(4) The template used in the present invention comprises a series of nanoparticles that can be removed by chemical methods, including but not limited to transition metal oxides such as ferroferric oxide, rare earth nanoparticles, silica particles, and the like.
(5) The method can also realize the preparation of ordered double-mesoporous carbon and graphene with different mesoporous morphologies, including three-dimensional spherical and two-dimensional film shapes, and the like, and is realized according to different assembly methods.
Drawings
FIG. 1 shows NaZn assembled from oleic acid ligand molecule-protected binary nanocrystals obtained in example 113Transmission electron micrograph of binary superlattice of structure.
FIG. 2 shows NaZn obtained in example 113Transmission electron microscopy of the structured bi-mesoporous graphene.
FIG. 3 shows NaZn obtained in example 113And (3) a transmission electron microscope image of the pore wall of the structured mesoporous bi-mesoporous graphene.
FIG. 4 shows NaZn obtained in example 113Raman spectrum of the structurally ordered double mesoporous graphene.
FIG. 5 shows NaZn obtained in example 113A small-angle X-ray scattering spectrogram of the morphological ordered double mesoporous graphene.
FIG. 6 shows NaZn obtained in example 113The nitrogen adsorption isotherm and the pore diameter distribution map of the morphological ordered double mesoporous graphene. Wherein: (a) is nitrogen adsorption isotherm, and (b) is pore size distribution.
Detailed Description
The present invention is described below by way of examples, but is not limited to these examples.
Example 1:
(1) ferroferric oxide colloid nanocrystalline particles with different sizes (2-20 nm) are selected and dispersed in solvents such as n-hexane/chloroform/toluene and the like to obtain colloid solution with the concentration of 10-80 mg/ml.
(2) The ferroferric oxide nanoparticles with the concentration of 15 nm and 8 nm, which are dispersed in n-hexane and have the concentration of 50 mg/ml, are taken as assembly units, and the molecular ligand of the ferroferric oxide nanoparticles is an oleic acid molecule. Co-assembling according to a specific 1:13 stoichiometric ratio to obtain a catalyst having NaZn13A binary superlattice of structure.
(3) And heating the obtained binary superlattice material to 350 ℃ at the heating rate of 2 ℃ per minute, keeping the temperature for 30 minutes for a short time, and then heating to 450 ℃ at the heating rate of 2 ℃ per minute for 120 minutes to convert the oleic acid molecular ligand on the particle surface into a three-dimensional through carbon coating.
(4) And (3) mixing 2 g of binary superlattice powder with 200 ml of 1M hydrochloric acid solution, and etching for 6 hours under the stirring of magnetons to remove the ferroferric oxide nano-particle template. Then, the product is subjected to suction filtration and centrifugal separation to obtain an etched powder sample, the etching is repeated for 2 times, and finally, the sample is cleaned by ethanol and deionized water to obtain the NaZn13An ordered double-mesoporous carbon material with a topological structure.
(5) Heating the ordered double-mesoporous carbon material to 1100 ℃ at the heating rate of 2 ℃ per minute, and keeping the temperature for 120 minutes to obtain the NaZn-containing carbon material13The specific surface area of the topological structure ordered double mesoporous graphene material 1 is 1152 m2G, pore volume 1.09 m3(ii)/g, pore size distribution 1.1 nm,4.8 nm and 8.8 nm.
Example 2:
(1) and taking 12 nm and 5 nm ferroferric oxide nanoparticles dispersed in chloroform and having the concentration of 80 mg/ml as assembly units, and converting oleic acid on the surfaces of the particles into oleoyl phosphate ligand molecules through ligand exchange. The AlB is obtained by the co-assembly according to the specific 1:2 stoichiometric ratio2A binary superlattice of structure.
(2) And (3) heating the template material to 400 ℃ at the heating rate of 1 ℃ per minute of the obtained binary superlattice material, keeping the temperature for 60 minutes, and then heating to 500 ℃ at the heating rate of 1 ℃ per minute for 60 minutes to convert the oleoyl phosphate molecular ligand on the particle surface into a three-dimensional through carbon coating.
(3) 0.5 g of binary nanocrystalline powder was mixed with 50 ml of 3M hydrochloric acid solution and etched for 4 hours under stirring by magnetons. Then, carrying out suction filtration and centrifugal separation on the product to obtain an etched powder sample, repeatedly etching for 3 times, and finally cleaning the sample by using ethanol and deionized water to obtain the product with AlB2An ordered double mesoporous carbon skeleton of topological structure.
(4) Heating the ordered double mesoporous carbon material to 1100 ℃ at the heating rate of 1 ℃ per minute, and keeping the temperature for 60 minutes to obtain AlB2The specific surface area of the topological structure ordered double mesoporous graphene material 2 is 1570 m2Per g, pore volume 2.02 m3(ii)/g, pore size distribution of 1.4 nm,3.8 nm and 8.0 nm.
Example 3:
(1) 7 nm and 10 nm ferroferric oxide nanoparticles dispersed in toluene at the concentration of 10 mg/ml are taken as assembly units, and the surfaces of the nanoparticles are oleic acid and oleylamine ligand molecules. Co-assembling according to a specific 1:2 stoichiometric ratio to obtain a magnesium zinc alloy with MgZn2A binary superlattice of structure.
(2) And heating the template material to 380 ℃ at the heating rate of 0.5 ℃ per minute for the obtained binary superlattice material, keeping the temperature for 40 minutes for a short time, and then heating to 430 ℃ at the heating rate of 0.5 ℃ per minute for 90 minutes to convert the organic micromolecule ligand on the particle surface into a three-dimensional through carbon coating.
(3) 1.0 g of binary nanocrystalline powder was mixed with 100 ml of 6M hydrochloric acid solution and etched for 8 hours under stirring by magnetons. Then, carrying out suction filtration and centrifugal separation on the product to obtain an etched powder sample, repeatedly etching for 4 times, and finally cleaning the sample by using ethanol and deionized water to obtain MgZn2An ordered double mesoporous carbon skeleton of a stacked structure.
(4) Heating the ordered dual-mesoporous carbon material to 1 ℃ at a heating rate of 3 ℃ per minuteKeeping the temperature at 500 ℃ for 90 minutes to obtain MgZn2Ordered double mesoporous graphene material 3 with a structure.
Claims (8)
1. A preparation method of an ordered double-mesoporous carbon graphene material or an ordered double-mesoporous carbon material is characterized by comprising the following steps:
(1) taking monodisperse colloid nano-particles with different sizes as an assembly unit, combining two kinds of nano-particles with effective particle diameter ratio, uniformly mixing the two kinds of nano-particles according to the chemical quantity ratio, and preparing a binary super-crystal by a co-assembly method;
(2) crosslinking and carbonizing the organic molecular ligand on the surface of the binary superlattice obtained in the step (1) by controlling the temperature of in-situ ligand carbonization;
(3) removing redundant nano particles on the surface of the product obtained in the step (2) by using acid solution etching to obtain an ordered double mesoporous carbon skeleton with a three-dimensional through structure;
(4) and (4) selecting a proper graphitization temperature, ensuring the stability of the ordered double-mesoporous framework obtained in the step (3), and simultaneously realizing graphitization of the carbon layer to obtain the ordered double-mesoporous graphene material or the ordered double-mesoporous carbon material with a topological structure.
2. The preparation method according to claim 1, wherein the monodisperse colloidal nanoparticles in step (1) have monodispersity and stability, the particle size is adjustable between 2 nm and 50 nm, the nanoparticles comprise inorganic nanoparticles capable of being completely removed by an acid solution, the surfaces of the nanoparticles are uniformly coated with oleic acid, oleylamine, thiol and oleoyl phosphate organic molecular ligands, the surfaces of the nanoparticles are exchanged into any molecular ligand through ligand exchange, and the nanoparticles can be placed in a solvent for a long time to keep colloidal stability and no precipitation.
3. The method according to claim 1, wherein the ratio of the effective particle diameters of the two kinds of nanoparticles in the step (1) is the effective particle diameter (R) of the nanoparticleeff) Can be regarded as the sum of the radius of the core (R) and the length of the ligand (L), i.e.Reff= R + L; the binary super-crystal can be prepared by combining nano-particles with the effective particle diameter ratio of 0.35-0.852、MgZn2、CuAu3、FeC4、CaCu5、CaB6Or NaZn13Any two-dimensional superlattice structure.
4. The preparation method according to claim 1, wherein the crosslinking temperature in step (2) is 300-400 ℃, the carbonization temperature is 400-520 ℃, the heating rate is kept at 0.5-10 ℃ per minute, and the constant temperature time for crosslinking and carbonization is 60-180 minutes.
5. The preparation method according to claim 1, wherein the concentration of the acid solution in the step (3) is 1-6 mol/L, and the etching is continuously performed for a plurality of times, so that the etching is guaranteed for more than 3 times.
6. The method according to claim 1, wherein the graphitization temperature in the step (4) is 900 ℃ or more, the heating rate is maintained at 0.5 to 10 ℃ per minute, and the constant temperature time is maintained at 60 to 180 minutes.
7. The preparation method according to claim 1, wherein the ordered bi-mesoporous graphene material obtained in step (4) is composed of large and small mesopores with sizes of 2-50 nm, which are interconnected according to a certain stacking manner to form a graphene skeleton, and the pore walls are composed of 3-6 layers of graphene.
8. The preparation method according to claim 1, wherein micropores are formed in the stacking gaps and the pore walls of the large and small mesopores in the ordered mesoporous graphene or mesoporous carbon obtained in step (4).
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