CN113353917A - Controllable preparation method of self-supporting two-dimensional mesoporous nano material - Google Patents
Controllable preparation method of self-supporting two-dimensional mesoporous nano material Download PDFInfo
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- XIOUDVJTOYVRTB-UHFFFAOYSA-N 1-(1-adamantyl)-3-aminothiourea Chemical compound C1C(C2)CC3CC2CC1(NC(=S)NN)C3 XIOUDVJTOYVRTB-UHFFFAOYSA-N 0.000 claims description 2
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- QGUAJWGNOXCYJF-UHFFFAOYSA-N cobalt dinitrate hexahydrate Chemical compound O.O.O.O.O.O.[Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O QGUAJWGNOXCYJF-UHFFFAOYSA-N 0.000 claims description 2
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/18—Carbon
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/06—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing polymers
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- B01J35/23—
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
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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
- C01B21/00—Nitrogen; Compounds thereof
- C01B21/06—Binary compounds of nitrogen with metals, with silicon, or with boron, or with carbon, i.e. nitrides; Compounds of nitrogen with more than one metal, silicon or boron
- C01B21/0605—Binary compounds of nitrogen with carbon
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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
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- C01B21/082—Compounds containing nitrogen and non-metals and optionally metals
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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
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- C01B32/15—Nano-sized carbon materials
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
Abstract
A controllable preparation method of a self-supporting two-dimensional mesoporous nano material belongs to the field of material structure regulation. It aims to solve the problems of severe reaction conditions, small specific surface area of products and few active sites in the existing process of constructing the two-dimensional mesoporous material with a sandwich structureAnd (5) problems are solved. The method comprises the following steps: preparing a two-dimensional nanostructure material; preparing F127-resol; preparation of two-dimensional F127-resol/MOF, graphene or gC3N4A composite structural material. The invention can effectively prevent the interlayer aggregation of the two-dimensional material, improves the contact specific surface area and catalytic active sites of ions, promotes the diffusion of the ions in the interlayer space, and has the advantages of good conductivity, full exposure of the active sites and the like. The method has the advantages of simple and mild synthesis conditions, no need of introducing strong corrosive or toxic materials such as hydrofluoric acid to take out the template to obtain the mesopores, small reaction implementation difficulty and environmental friendliness. The material obtained by the invention is used as a carbon-based electrocatalyst.
Description
Technical Field
The invention belongs to the field of material structure regulation and control, and particularly relates to a controllable preparation method of a self-supporting two-dimensional mesoporous nano material.
Background
In recent years, nanostructures with two-dimensional (2D) morphology, such as graphene-based nanoplatelets, Metal Organic Framework (MOFs) nanoplatelets or nanoplates, two-dimensional graphite-phase carbon nitride g-C3N4The materials have received much attention due to their unique structural and electrical and optical properties. The two-dimensional MOF material has a large surface area and rich framework composition, and the open structure of the material provides more active sites to accelerate the interaction processes of internal ion adsorption, diffusion, separation, transportation and the like, so that the material has a remarkable application value in the fields of energy conversion and storage, catalysis, electrochemistry and the like. However, in practical applications, self-accumulation of most two-dimensional materials inevitably occurs, which results in low specific surface area, poor conductivity, reduction of catalytic sites for transporting ion contacts, inhibition of ion diffusion, and thus the excellent properties of the two-dimensional nanomaterials are not fully utilized. Therefore, an engineering strategy for effectively regulating and controlling the two-dimensional nanosheet structure is needed, so that the basic characteristics of the nanosheet structure are retained to the greatest extent. In order to achieve the purpose, some researchers use a hard template or a soft template to construct a two-dimensional mesoporous material with a sandwich structure, but for example, a mesoporous carbon catalyst constructed by graphene-based silica nanospheres needs to use highly corrosive hydrofluoric acid when removing silica. Therefore, a method for developing a porous energy material with a two-dimensional composite structure, which has mild reaction conditions and is environmentally friendly, is sought.
Disclosure of Invention
The invention aims to provide a controllable preparation method of a self-supporting two-dimensional mesoporous nano material, which aims to solve the problems of severe reaction conditions, small specific surface area of a product and few active sites in the existing process of constructing a two-dimensional sandwich structure mesoporous material.
The controllable preparation method of the self-supporting two-dimensional mesoporous nano material is realized by the following steps:
firstly, preparing MOF nano-plates:
dissolving 0.98mg of surfactant in 5mL of deionized water, then adding 1.06g of 2-methylimidazole, and carrying out ultrasonic treatment until the 2-methylimidazole is completely dissolved to obtain a mixed solution; dissolving 0.3g of metal salt in 5mL of deionized water, then carrying out mixed reaction with the mixed solution, magnetically stirring for 15-30 s, standing for 2-6 h, and centrifugally washing with deionized water to obtain an MOF nano plate;
secondly, preparing F127-resol:
taking 0.6g of phenol, stirring at 50 ℃ until the phenol is melted, dropwise adding 15mL of 0.1M sodium hydroxide solution, stirring until the temperature is stabilized at 70 ℃, dropwise adding 2.1mL of 37 wt% formaldehyde solution, stirring for 30min, then adding 15mL of 0.96g of F127 solution, keeping the temperature stabilized at 66 ℃, stirring for 2h, adding 50mL of deionized water, keeping the temperature at 70 ℃, stirring for 12-16 h, and taking out to obtain F127-resol (namely block copolymer-phenolic resin);
and thirdly, preparing the two-dimensional F127-cool/MOF composite structure nano plate:
mixing the Resol-F127 and the MOF nano-plate, adding deionized water to a constant volume of 35mL, placing the mixture in a reaction kettle, mixing and stirring for 30min, standing for 12h, performing hydrothermal reaction at 100-130 ℃ for 22-24 h, then respectively performing centrifugal washing with the ionized water and absolute ethyl alcohol, and freeze-drying for 12h after washing to obtain a two-dimensional F127-Resol/MOF composite structure nano-plate;
fourthly, preparing the self-supporting two-dimensional mesoporous nano material:
and (2) placing the two-dimensional F127-cool/MOF composite structure nano plate in a porcelain boat, then placing the porcelain boat in a tube furnace, heating to 350 ℃ in a nitrogen atmosphere, keeping the temperature constant for 1h, heating to 900 ℃ and keeping the temperature constant for 3h, and then cooling along with the furnace to finish the controllable preparation of the self-supporting two-dimensional mesoporous nano material.
The controllable preparation method of the self-supporting two-dimensional mesoporous nano material can be realized by the following steps:
firstly, preparing F127-resol:
taking 0.6g of phenol, stirring at 50 ℃ until the phenol is melted, dropwise adding 15mL of 0.1M sodium hydroxide solution, stirring until the temperature is stabilized at 70 ℃, dropwise adding 2.1mL of 37 wt% formaldehyde solution, stirring for 30min, then adding 15mL of 0.96g of F127 solution, keeping the temperature stabilized at 66 ℃, stirring for 2h, adding 50mL of deionized water, keeping the temperature at 70 ℃, stirring for 12-16 h, and taking out to obtain F127-resol;
two, two dimensional F127-resol/g-C3N4Preparing a composite structure material:
30g of urea is placed in a covered crucible and sintered for 2 hours at the high temperature of 550 ℃ in a tube furnace to obtain g-C3N460mg of g-C3N4Mixing with 3mL of F127-resol, adding deionized water to a constant volume of 18mL, placing in a reaction kettle, mixing and stirring for 30min, standing for 12h, performing hydrothermal reaction at 100-130 ℃ for 22-24 h, respectively performing centrifugal washing with ionized water and absolute ethyl alcohol, and freeze-drying for 12h after washing to obtain two-dimensional F127-resol/g-C3N4The controllable preparation of the self-supporting two-dimensional mesoporous nano material is completed.
The controllable preparation method of the self-supporting two-dimensional mesoporous nano material can be realized by the following steps:
firstly, preparing F127-resol:
taking 0.6g of phenol, stirring at 50 ℃ until the phenol is melted, dropwise adding 15mL of 0.1M sodium hydroxide solution, stirring until the temperature is stabilized at 70 ℃, dropwise adding 2.1mL of 37 wt% formaldehyde solution, stirring for 30min, then adding 15mL of 0.96g of F127 solution, keeping the temperature stabilized at 66 ℃, stirring for 2h, adding 50mL of deionized water, keeping the temperature at 70 ℃, stirring for 12-16 h, and taking out to obtain F127-resol;
secondly, preparing a two-dimensional F127-cool/graphene composite structure material:
mixing 1mL of graphene oxide with the concentration of 2mg/mL with 1mL of F127-resol, adding deionized water to a constant volume of 15mL, placing the mixture in a reaction kettle, mixing and stirring for 30min, standing for 12h, carrying out hydrothermal reaction at 100-130 ℃ for 22-24 h, then respectively carrying out centrifugal washing with the ionized water and absolute ethyl alcohol, and carrying out freeze drying for 12h after washing to obtain a two-dimensional F127-resol/graphene composite structure material, thus completing the controllable preparation of the self-supporting two-dimensional mesoporous nano material.
The invention has the beneficial effects that:
the invention relates to a controllable preparation method of a self-supporting two-dimensional mesoporous nano material, which is to mix two-dimensional nano structure materials such as MOF and g-C3N4Or the graphene is used as a hard template, the block copolymer-phenolic resin is used as a soft template, and the block copolymer-phenolic resin has a monodisperse spherical structure; the soft and hard template is adopted to assist in preparing the unconventional ordered mesoporous material, and F127-resol micelle globules are adsorbed on the surface of the two-dimensional nano-structure material through electrostatic adsorption to form monodisperse globules which are arranged in order.
The mesoporous energy catalytic material with the composite two-dimensional sandwich structure is obtained by inducing micelles to be orderly self-assembled and arranged on a two-dimensional sheet layer. The self-supporting block copolymer is introduced in the invention, so that the interlayer agglomeration of the two-dimensional material can be effectively prevented, the two-dimensional nanostructure material can be fully utilized, the mesoporous layer on the surface not only improves the contact specific surface area and catalytic active sites of ions, but also promotes the diffusion of the ions in the interlayer space, and the preparation method has the advantages of good conductivity, full exposure of the active sites and the like, and is particularly suitable for the application of an electrocatalyst.
The preparation method has the advantages of simple reaction system, low cost of reaction reagents, simple and mild synthesis conditions, no need of introducing strong corrosive or toxic materials such as hydrofluoric acid to take out the template to obtain the mesopores, low reaction implementation difficulty and environmental friendliness.
The self-supporting two-dimensional mesoporous nano material is used as a non-noble metal carbon-based electrocatalyst with low cost, high activity and stability, and is applied to oxidation-reduction reaction, oxygen evolution reaction and hydrogen evolution reaction.
Drawings
FIG. 1 is a scanning electron microscope image of the MOF nanoplates of example 1;
FIG. 2 is a scanning electron microscope photograph of the MOF nanoplates of example 1 after carbon calcination;
FIG. 3 is a scanning electron microscope image of the two-dimensional F127-cool/MOF composite structure nanoplates of example 1;
FIG. 4 is a scanning electron microscope photograph of the two-dimensional F127-cool/MOF composite structured nano-plate of example 1 after carbon burning;
FIG. 5 is a TEM image of the two-dimensional F127-cool/MOF composite structure nano-plate in example 1 after carbon burning;
FIG. 6 is a two-dimensional F127-resol/g-C in example 23N4Scanning electron microscopy of the composite structural material;
FIG. 7 is a scanning electron microscope image of the two-dimensional F127-cool/graphene composite structure material in example 3.
Detailed Description
The first embodiment is as follows: the controllable preparation method of the self-supporting two-dimensional mesoporous nano material is realized according to the following steps:
firstly, preparing MOF nano-plates:
dissolving 0.98mg of surfactant in 5mL of deionized water, then adding 1.06g of 2-methylimidazole, and carrying out ultrasonic treatment until the 2-methylimidazole is completely dissolved to obtain a mixed solution; dissolving 0.3g of metal salt in 5mL of deionized water, then carrying out mixed reaction with the mixed solution, magnetically stirring for 15-30 s, standing for 2-6 h, and centrifugally washing with deionized water to obtain an MOF nano plate;
secondly, preparing F127-resol:
taking 0.6g of phenol, stirring at 50 ℃ until the phenol is melted, dropwise adding 15mL of 0.1M sodium hydroxide solution, stirring until the temperature is stabilized at 70 ℃, dropwise adding 2.1mL of 37 wt% formaldehyde solution, stirring for 30min, then adding 15mL of 0.96g of F127 solution, keeping the temperature stabilized at 66 ℃, stirring for 2h, adding 50mL of deionized water, keeping the temperature at 70 ℃, stirring for 12-16 h, and taking out to obtain F127-resol (namely block copolymer-phenolic resin);
and thirdly, preparing the two-dimensional F127-cool/MOF composite structure nano plate:
mixing the Resol-F127 and the MOF nano-plate, adding deionized water to a constant volume of 35mL, placing the mixture in a reaction kettle, mixing and stirring for 30min, standing for 12h, performing hydrothermal reaction at 100-130 ℃ for 22-24 h, then respectively performing centrifugal washing with the ionized water and absolute ethyl alcohol, and freeze-drying for 12h after washing to obtain a two-dimensional F127-Resol/MOF composite structure nano-plate;
fourthly, preparing the self-supporting two-dimensional mesoporous nano material:
and (2) placing the two-dimensional F127-cool/MOF composite structure nano plate in a porcelain boat, then placing the porcelain boat in a tube furnace, heating to 350 ℃ in a nitrogen atmosphere, keeping the temperature constant for 1h, heating to 900 ℃ and keeping the temperature constant for 3h, and then cooling along with the furnace to finish the controllable preparation of the self-supporting two-dimensional mesoporous nano material.
The second embodiment is as follows: unlike the first embodiment, the surfactant in the first embodiment is cetyltrimethylammonium bromide (CTAB). Other steps and parameters are the same as those in the first embodiment.
The third concrete implementation mode: the difference between this embodiment and the first or second embodiment is that, in the first step, the metal salt is zinc acetate, cobalt acetate, zinc nitrate hexahydrate or cobalt nitrate hexahydrate. Other steps and parameters are the same as those in the first or second embodiment.
The fourth concrete implementation mode: the difference between this embodiment and one of the first to third embodiments is that in the first step, the mixture is magnetically stirred for 20 seconds and then is left standing for 4 hours. Other steps and parameters are the same as those in one of the first to third embodiments.
The fifth concrete implementation mode: the difference between this embodiment and one of the first to the fourth embodiments is that the concentration of F127 in the F127-pool obtained in the second step is 12 mg/mL. Other steps and parameters are the same as in one of the first to fourth embodiments.
The sixth specific implementation mode: the difference between this embodiment and one of the first to fifth embodiments is that the mass ratio of the MOF nano-plates to the Resol-F127 in step three is 7.5:1 or 2.5: 1. Other steps and parameters are the same as those in one of the first to fifth embodiments.
The seventh embodiment: the difference between this embodiment and one of the first to sixth embodiments is that the mixture is allowed to stand for 12 hours in the third step and then undergoes hydrothermal reaction at 120 ℃ for 23 hours. Other steps and parameters are the same as those in one of the first to sixth embodiments.
The specific implementation mode is eight: the difference between this embodiment and one of the first to seventh embodiments is that the heating rate in step four is 2 ℃/min. Other steps and parameters are the same as those in one of the first to seventh embodiments.
The specific implementation method nine: the controllable preparation method of the self-supporting two-dimensional mesoporous nano material can be realized by the following steps:
firstly, preparing F127-resol:
taking 0.6g of phenol, stirring at 50 ℃ until the phenol is melted, dropwise adding 15mL of 0.1M sodium hydroxide solution, stirring until the temperature is stabilized at 70 ℃, dropwise adding 2.1mL of 37 wt% formaldehyde solution, stirring for 30min, then adding 15mL of 0.96g of F127 solution, keeping the temperature stabilized at 66 ℃, stirring for 2h, adding 50mL of deionized water, keeping the temperature at 70 ℃, stirring for 12-16 h, and taking out to obtain F127-resol;
two, two dimensional F127-resol/g-C3N4Preparing a composite structure material:
30g of urea is placed in a covered crucible and sintered for 2 hours at the high temperature of 550 ℃ in a tube furnace to obtain g-C3N460mg of g-C3N4Mixing with 3mL of F127-resol, adding deionized water to a constant volume of 18mL, placing in a reaction kettle, mixing and stirring for 30min, standing for 12h, performing hydrothermal reaction at 100-130 ℃ for 22-24 h, respectively performing centrifugal washing with ionized water and absolute ethyl alcohol, and freeze-drying for 12h after washing to obtain two-dimensional F127-resol/g-C3N4The controllable preparation of the self-supporting two-dimensional mesoporous nano material is completed.
The detailed implementation mode is ten: the difference between this embodiment and the ninth embodiment is that the concentration of F127 in the F127-resol obtained in the first step is 12 mg/mL. Other steps and parameters are the same as those in the ninth embodiment.
The concrete implementation mode eleven: the controllable preparation method of the self-supporting two-dimensional mesoporous nano material can be realized by the following steps:
firstly, preparing F127-resol:
taking 0.6g of phenol, stirring at 50 ℃ until the phenol is melted, dropwise adding 15mL of 0.1M sodium hydroxide solution, stirring until the temperature is stabilized at 70 ℃, dropwise adding 2.1mL of 37 wt% formaldehyde solution, stirring for 30min, then adding 15mL of 0.96g of F127 solution, keeping the temperature stabilized at 66 ℃, stirring for 2h, adding 50mL of deionized water, keeping the temperature at 70 ℃, stirring for 12-16 h, and taking out to obtain F127-resol;
secondly, preparing a two-dimensional F127-cool/graphene composite structure material:
mixing 1mL of graphene oxide with the concentration of 2mg/mL with 1mL of F127-resol, adding deionized water to a constant volume of 15mL, placing the mixture in a reaction kettle, mixing and stirring for 30min, standing for 12h, carrying out hydrothermal reaction at 100-130 ℃ for 22-24 h, then respectively carrying out centrifugal washing with the ionized water and absolute ethyl alcohol, and carrying out freeze drying for 12h after washing to obtain a two-dimensional F127-resol/graphene composite structure material, thus completing the controllable preparation of the self-supporting two-dimensional mesoporous nano material.
The specific implementation mode twelve: the difference between this embodiment and the eleventh embodiment is that the concentration of F127 in the F127-resol obtained in the first step is 12 mg/mL. Other steps and parameters are the same as those in the eleventh embodiment.
The beneficial effects of the present invention are demonstrated by the following examples:
example 1:
the controllable preparation method of the self-supporting two-dimensional mesoporous nano material is realized by the following steps:
firstly, preparing MOF nano-plates:
dissolving 0.98mg of hexadecyl trimethyl ammonium bromide in 5mL of deionized water, then adding 1.06g of 2-methylimidazole, and carrying out ultrasonic treatment until complete dissolution to obtain a mixed solution; dissolving 0.3g of zinc acetate in 5mL of deionized water, then carrying out mixed reaction with the mixed solution, magnetically stirring for 30s, standing for 5h, and centrifugally washing with deionized water to obtain an MOF nano plate;
secondly, preparing F127-resol:
taking 0.6g of phenol, stirring at 50 ℃ until the phenol is melted, dropwise adding 15mL of 0.1M sodium hydroxide solution, stirring until the temperature is stabilized at 70 ℃, dropwise adding 2.1mL of 37 wt% formaldehyde solution, stirring for 30min, then adding 15mL of 0.96g of F127 solution, keeping the temperature stabilized at 66 ℃, stirring for 2h, adding 50mL of deionized water, keeping the temperature at 70 ℃, stirring for 14h, and taking out to obtain F127-resol;
and thirdly, preparing the two-dimensional F127-cool/MOF composite structure nano plate:
mixing the Resol-F127 and the MOF nano-plate, adding deionized water to a constant volume of 35mL, placing the mixture in a reaction kettle, mixing and stirring for 30min, standing for 12h, performing hydrothermal reaction at 120 ℃ for 23h, then respectively performing centrifugal washing by using ionized water and absolute ethyl alcohol, and performing freeze drying for 12h after washing to obtain a two-dimensional F127-Resol/MOF composite structure nano-plate;
fourthly, preparing the self-supporting two-dimensional mesoporous nano material:
and (2) placing the two-dimensional F127-cool/MOF composite structure nano plate in a porcelain boat, then placing the porcelain boat in a tube furnace, heating to 350 ℃ in a nitrogen atmosphere, keeping the temperature constant for 1h, heating to 900 ℃ and keeping the temperature constant for 3h, and then cooling along with the furnace to finish the controllable preparation of the self-supporting two-dimensional mesoporous nano material.
The concentration of F127 in the F127-pool obtained in step two of this example was 12 mg/mL.
In the third step of this example, the mass ratio of the MOF nano-plate to the Resol-F127 was 7.5: 1.
In the fourth step of this example, the heating rate was 2 ℃/min.
The MOF nanoplates obtained in step one of this example were about 800nm in diameter, as shown in fig. 1; if the MOF nanoplates are carbonized directly, most of the nanoplates are stacked, as shown in fig. 2, although the size of the MOF is retained in the carbon-based nanostructures.
In the two-dimensional F127-pool/MOF composite structure nano-plate obtained in the third step of this embodiment, as shown in FIG. 3, after the F127-pool micelle is modified, the MOF still maintains the ductility of two-dimensional scale, and meanwhile, the micelle globules are uniformly and orderly modified on the surface and edge of the MOF nano-plate.
After carbonization in the fourth step of this embodiment, as shown in fig. 4 and 5, the carbon-based nanosheets still maintain the morphology of the composite structure after high-temperature sintering, and the carbon-based nanosheets have a two-dimensional sandwich structure and are in sheetsAnd the effective contact area with the outside is increased due to the gap between the sheets. Meanwhile, the specific surface area test shows that the specific surface area of the MOF nano plate modified by the F127-resol micelle is 337m2g-1Is lifted to 616m2g-1Pore volume from 0.37cm3g-1Lifting to 0.63cm3g-1After the MOF nano plate modified by the F127-resol micelle is subjected to high-temperature carbon burning, the surface of the MOF nano plate presents a clear pore structure, and the size of most of pore materials belongs to the mesoporous range.
In the embodiment, the MOF material is prepared by a wet chemical method, and is a nanometer plate with a ZIF-8 structure and taking zinc metal salt as a precursor, which is different from a polyhedral structure, wherein the ZIF-8 has a metal framework structure extending on a two-dimensional scale. The block copolymer-phenolic resin (F127-resol) is used as a soft template, and the composite micelle has a monodisperse spherical structure. The two-dimensional F127-resol/MOF composite structure nano plate takes a polymer as a soft template, MOF as a hard template, and F127-resol micelle globules are adsorbed on the surface of the MOF by the soft and hard templates through electrostatic adsorption to form orderly arranged monodisperse globules. The two-dimensional composite porous structure carbon-based electrocatalyst can convert a two-dimensional F127-cool/MOF composite structure nano plate into a two-dimensional sandwich structure porous carbon-based nano plate by high-temperature carbonization.
Example 2:
the controllable preparation method of the self-supporting two-dimensional mesoporous nano material can be realized by the following steps:
firstly, preparing F127-resol:
taking 0.6g of phenol, stirring at 50 ℃ until the phenol is melted, dropwise adding 15mL of 0.1M sodium hydroxide solution, stirring until the temperature is stabilized at 70 ℃, dropwise adding 2.1mL of 37 wt% formaldehyde solution, stirring for 30min, then adding 15mL of 0.96g of F127 solution, keeping the temperature stabilized at 66 ℃, stirring for 2h, adding 50mL of deionized water, keeping the temperature at 70 ℃, stirring for 12-16 h, and taking out to obtain F127-resol;
two, two dimensional F127-resol/g-C3N4Preparing a composite structure material:
placing 30g of urea in a covered crucible, and sintering at 550 ℃ for 2h in a tube furnace to obtainTo g-C3N460mg of g-C3N4Mixing with 3mL of F127-resol, adding deionized water to a constant volume of 18mL, placing in a reaction kettle, mixing and stirring for 30min, standing for 12h, performing hydrothermal reaction at 100-130 ℃ for 22-24 h, respectively performing centrifugal washing with ionized water and absolute ethyl alcohol, and freeze-drying for 12h after washing to obtain two-dimensional F127-resol/g-C3N4The controllable preparation of the self-supporting two-dimensional mesoporous nano material is completed.
The concentration of F127 in the F127-pool obtained in the first step of this example was 12 mg/mL.
Two-dimensional F127-resol/g-C obtained in this example3N4As shown in FIG. 6, micelle globules are distributed on the surface of the two-dimensional material in order after the composite structural material is modified by F127-resol.
Example 3:
the controllable preparation method of the self-supporting two-dimensional mesoporous nano material can be realized by the following steps:
firstly, preparing F127-resol:
taking 0.6g of phenol, stirring at 50 ℃ until the phenol is melted, dropwise adding 15mL of 0.1M sodium hydroxide solution, stirring until the temperature is stabilized at 70 ℃, dropwise adding 2.1mL of 37 wt% formaldehyde solution, stirring for 30min, then adding 15mL of 0.96g of F127 solution, keeping the temperature stabilized at 66 ℃, stirring for 2h, adding 50mL of deionized water, keeping the temperature at 70 ℃, stirring for 12-16 h, and taking out to obtain F127-resol;
secondly, preparing a two-dimensional F127-cool/graphene composite structure material:
mixing 1mL of graphene oxide with the concentration of 2mg/mL with 1mL of F127-resol, adding deionized water to a constant volume of 15mL, placing the mixture in a reaction kettle, mixing and stirring for 30min, standing for 12h, carrying out hydrothermal reaction at 100-130 ℃ for 22-24 h, then respectively carrying out centrifugal washing with the ionized water and absolute ethyl alcohol, and carrying out freeze drying for 12h after washing to obtain a two-dimensional F127-resol/graphene composite structure material, thus completing the controllable preparation of the self-supporting two-dimensional mesoporous nano material.
The concentration of F127 in the F127-pool obtained in the first step of this example was 12 mg/mL.
The two-dimensional F127-pool/graphene composite structure material obtained in the embodiment is shown in FIG. 7, and micelle globules are orderly distributed on the surface of the two-dimensional material after the two-dimensional material is modified by the F127-pool.
Claims (10)
1. The controllable preparation method of the self-supporting two-dimensional mesoporous nano material is characterized by comprising the following steps of:
firstly, preparing MOF nano-plates:
dissolving 0.98mg of surfactant in 5mL of deionized water, then adding 1.06g of 2-methylimidazole, and carrying out ultrasonic treatment until the 2-methylimidazole is completely dissolved to obtain a mixed solution; dissolving 0.3g of metal salt in 5mL of deionized water, then carrying out mixed reaction with the mixed solution, magnetically stirring for 15-30 s, standing for 2-6 h, and centrifugally washing with deionized water to obtain an MOF nano plate;
secondly, preparing F127-resol:
taking 0.6g of phenol, stirring at 50 ℃ until the phenol is melted, dropwise adding 15mL of 0.1M sodium hydroxide solution, stirring until the temperature is stabilized at 70 ℃, dropwise adding 2.1mL of 37 wt% formaldehyde solution, stirring for 30min, then adding 15mL of 0.96g of F127 solution, keeping the temperature stabilized at 66 ℃, stirring for 2h, adding 50mL of deionized water, keeping the temperature at 70 ℃, stirring for 12-16 h, and taking out to obtain F127-resol;
and thirdly, preparing the two-dimensional F127-cool/MOF composite structure nano plate:
mixing the Resol-F127 and the MOF nano-plate, adding deionized water to a constant volume of 35mL, placing the mixture in a reaction kettle, mixing and stirring for 30min, standing for 12h, performing hydrothermal reaction at 100-130 ℃ for 22-24 h, then respectively performing centrifugal washing with the ionized water and absolute ethyl alcohol, and freeze-drying for 12h after washing to obtain a two-dimensional F127-Resol/MOF composite structure nano-plate;
fourthly, preparing the self-supporting two-dimensional mesoporous nano material:
and (2) placing the two-dimensional F127-cool/MOF composite structure nano plate in a porcelain boat, then placing the porcelain boat in a tube furnace, heating to 350 ℃ in a nitrogen atmosphere, keeping the temperature constant for 1h, heating to 900 ℃ and keeping the temperature constant for 3h, and then cooling along with the furnace to finish the controllable preparation of the self-supporting two-dimensional mesoporous nano material.
2. The controllable preparation method of self-supporting two-dimensional mesoporous nano material according to claim 1, wherein the surfactant in the first step is cetyl trimethyl ammonium bromide.
3. The controllable preparation method of the self-supporting two-dimensional mesoporous nanomaterial according to claim 1, wherein the metal salt in the first step is zinc acetate, cobalt acetate, zinc nitrate hexahydrate or cobalt nitrate hexahydrate.
4. The controllable preparation method of the self-supporting two-dimensional mesoporous nano material of claim 1, wherein the concentration of F127 in the F127-cool obtained in the second step is 12 mg/mL.
5. The controllable preparation method of the self-supporting two-dimensional mesoporous nano material according to claim 1, characterized in that the mass ratio of the MOF nano plates to the Resol-F127 in the third step is 7.5:1 or 2.5: 1.
6. The controllable preparation method of the self-supporting two-dimensional mesoporous nano material according to claim 1, characterized in that the hydrothermal reaction is carried out for 23h at 120 ℃ after the standing for 12h in the third step.
7. The controllable preparation method of the self-supporting two-dimensional mesoporous nano material according to claim 1, wherein the heating rate in the fourth step is 2 ℃/min.
8. The controllable preparation method of the self-supporting two-dimensional mesoporous nano material is characterized by also comprising the following steps of:
firstly, preparing F127-resol:
taking 0.6g of phenol, stirring at 50 ℃ until the phenol is melted, dropwise adding 15mL of 0.1M sodium hydroxide solution, stirring until the temperature is stabilized at 70 ℃, dropwise adding 2.1mL of 37 wt% formaldehyde solution, stirring for 30min, then adding 15mL of 0.96g of F127 solution, keeping the temperature stabilized at 66 ℃, stirring for 2h, adding 50mL of deionized water, keeping the temperature at 70 ℃, stirring for 12-16 h, and taking out to obtain F127-resol;
two, two dimensional F127-resol/g-C3N4Preparing a composite structure material:
30g of urea is placed in a covered crucible and sintered for 2 hours at the high temperature of 550 ℃ in a tube furnace to obtain g-C3N460mg of g-C3N4Mixing with 3mL of F127-resol, adding deionized water to a constant volume of 18mL, placing in a reaction kettle, mixing and stirring for 30min, standing for 12h, performing hydrothermal reaction at 100-130 ℃ for 22-24 h, respectively performing centrifugal washing with ionized water and absolute ethyl alcohol, and freeze-drying for 12h after washing to obtain two-dimensional F127-resol/g-C3N4The controllable preparation of the self-supporting two-dimensional mesoporous nano material is completed.
9. The controllable preparation method of the self-supporting two-dimensional mesoporous nano material of claim 8, wherein the concentration of F127 in the F127-cool obtained in the first step is 12 mg/mL.
10. The controllable preparation method of the self-supporting two-dimensional mesoporous nano material is characterized by also comprising the following steps of:
firstly, preparing F127-resol:
taking 0.6g of phenol, stirring at 50 ℃ until the phenol is melted, dropwise adding 15mL of 0.1M sodium hydroxide solution, stirring until the temperature is stabilized at 70 ℃, dropwise adding 2.1mL of 37 wt% formaldehyde solution, stirring for 30min, then adding 15mL of 0.96g of F127 solution, keeping the temperature stabilized at 66 ℃, stirring for 2h, adding 50mL of deionized water, keeping the temperature at 70 ℃, stirring for 12-16 h, and taking out to obtain F127-resol;
secondly, preparing a two-dimensional F127-cool/graphene composite structure material:
mixing 1mL of graphene oxide with the concentration of 2mg/mL with 1mL of F127-resol, adding deionized water to a constant volume of 15mL, placing the mixture in a reaction kettle, mixing and stirring for 30min, standing for 12h, carrying out hydrothermal reaction at 100-130 ℃ for 22-24 h, then respectively carrying out centrifugal washing with the ionized water and absolute ethyl alcohol, and carrying out freeze drying for 12h after washing to obtain a two-dimensional F127-resol/graphene composite structure material, thus completing the controllable preparation of the self-supporting two-dimensional mesoporous nano material.
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