CN111892034A - Mass production method of long-range ordered mesoporous carbon/mesoporous silicon material with ultrahigh specific surface area - Google Patents
Mass production method of long-range ordered mesoporous carbon/mesoporous silicon material with ultrahigh specific surface area Download PDFInfo
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Abstract
The invention discloses a mass production method of a long-range ordered mesoporous carbon/mesoporous silicon material with ultrahigh specific surface area, which comprises the steps of coating, curing, pre-firing, high-temperature sintering, crushing and ball-milling a raw material mixture containing phenolic resin, tetraethoxysilane and F127 to particles, soaking in alkali liquor, heating and then cleaning. Chemical products with stable yield and low price are adopted as raw materials, and the process steps are simple and easy to implement, so that the cost can be greatly reduced, and the large-scale industrial application of mesoporous materials is facilitated; more importantly, the prepared mesoporous carbon and mesoporous silicon materials have the advantages of long-range order, stable structure, uniform pore channels and large specific surface area, and can be used for multiple purposes of energy materials, adsorption materials and catalytic materials.
Description
Technical Field
The invention belongs to the field of nano materials, relates to mesoporous carbon or mesoporous silicon materials, and particularly relates to a mass production method of long-range ordered mesoporous carbon/mesoporous silicon materials with ultrahigh specific surface area
Background
With the development of high and new technology industries, especially the development of 5G technology, electronic technology and information industry, people need new materials with higher performance as basic guarantees. Nanotechnology and nanomaterials have gained wide attention in the industry and academia as new materials in the 21 st century. Ordered mesoporous materials have attracted great interest in the chemical, physical, material and biological industries as a popular field in the field of nanomaterials.
The ordered mesoporous material is an inorganic porous material which has a pore diameter of 2-30 nm, narrow pore diameter distribution and a regular pore channel structure and is assembled by taking a supermolecular structure formed by a surfactant as a template and utilizing a sol-gel process through the directional action between an organic matter interface and an inorganic matter interface. The porous membrane has the characteristics of uniform pore size, ordered arrangement, continuously adjustable pore diameter within the range of 2-50 nm and the like, so that the porous membrane has great application potential in the aspects of separation and purification, biological materials, catalysis, novel assembly materials and the like.
The synthesis of ordered mesoporous materials has been started as early as 1971, but the Mobil company has not attracted attention until 1992 and is considered to be the start of the synthesis of ordered mesoporous materials. Scientists have used surfactant as molecular template to synthesize M41S series mesoporous materials, including MCM-41 (hexagonal phase), MCM-48 (cubic phase) and MCM-50 (lamellar structure), which is an improvement over Mobil's scientists in the 20 th century and 70 th era, and the successful synthesis of ZSM-5. Both of these examples are porous materials with specific molecular sieve properties obtained by controlling the size and shape of the channels and limiting the size of the reactants to below about 1 nm; even through the modification of the pore channel, the pore diameter is limited, and the appearance of the mesoporous material provides possibility for solving the problems.
The mesoporous material has regular mesoporous channels (2-50 nm), larger specific surface area and channel volume, which are the characteristics and structural advantages of the mesoporous material, and on the other hand, the mesoporous channels are formed by amorphous pore walls, so that compared with microporous molecular sieves, the mesoporous material has lower thermal stability and hydrothermal stability, and the defects in the aspects of SBA-15, MAS-7 and MAS-9 are improved to a certain extent in recent years. However, mesoporous materials have the special advantage that the limitation of the framework atoms is much smaller than that of zeolites, and theoretically, any oxide or oxide compound, inorganic compound or even metal can be used as the mesoporous material compound, and in fact, various non-silicon mesoporous materials such as TiO have been synthesized2、ZrO2、Al2O3、Ga2O3And the like.
However, the production of these ordered mesoporous materials is usually done in batches in the laboratory. The laboratory equipment and process are limited, the product yield is greatly limited, and the product performance difference among different batches is difficult to control. During the production process, if a larger-sized container is used, the mesoporous structure of the product is affected. For a kilogram-level process for producing mesoporous carbon, polyurethane foam can be used as a 3D support, but the method is only limited to preparation of mesoporous carbon materials; also, the speed of the production process is limited by solvent evaporation from the polyurethane foam cells. In addition, a hard template method can be used for preparing the ordered mesoporous carbon material, but the hard template method relates to multiple steps of template agent self-assembly, carbon source pouring, carbonization, template agent removal and the like, and has high cost; and the proportion of the carbon source and the template and the pouring process need to be accurately controlled, otherwise, the disorder of partial structures can be caused. In view of the higher control capability requirement of the mesoporous carbon on the microporous structure and the limited productivity, the open selling price of the ordered mesoporous carbon is 1200-1800 yuan/g at present, which greatly exceeds the price range widely applied in the industry. Therefore, a rapid, effective, stable and controllable process suitable for large-scale mass production of various mesoporous materials is urgently needed for realizing commercialization of the mesoporous materials.
Disclosure of Invention
Aiming at the defects in the prior art, the invention provides a mass production method of long-range ordered mesoporous carbon/mesoporous silicon material with ultrahigh specific surface area.
The first purpose of the invention is to provide a mass production method of long-range ordered mesoporous carbon/mesoporous silicon material with ultrahigh specific surface area, which is characterized in that: coating, curing, pre-sintering, high-temperature sintering and crushing a raw material mixture containing phenolic resin, tetraethoxysilane and F127;
when the product to be produced is mesoporous silicon carbon, performing ball milling to obtain particles;
when the product to be produced is mesoporous carbon, ball-milling the mesoporous carbon to particles, soaking the particles in alkali liquor, heating and cleaning the particles;
when the product to be produced in mass is mesoporous silicon, the mesoporous silicon is also ball-milled to particles and calcined in air or oxygen atmosphere.
Optimally, the mass ratio of the phenolic resin to the tetraethoxysilane to the F127 is 1: 2: 1.
further, it comprises the following steps:
(a) adding the phenolic resin, the ethyl orthosilicate, the F127 and 0.1 mol/L hydrochloric acid into an organic solvent, and heating and stirring at 30-50 ℃ for 3-5 hours to obtain a first solution;
(b) coating the first solution with a film;
(c) carrying out gradient temperature rise on the film obtained in the step (b) within the temperature range of 40-60 ℃, and standing for 6-12 hours;
(d) carrying out gradient temperature rise on the film obtained in the step (c) within a temperature range of 90-100 ℃, and standing for 6-12 hours;
(e) calcining the film obtained in the step (d) at a high temperature of 750-850 ℃ for 3-5 hours in an inert gas atmosphere;
(f) crushing the calcined material obtained in the step (e) to an average particle size of 2-3 mm, and ball-milling the crushed material to an average particle size of 1-10 μm;
or, further comprising: (g) putting the ball-milling material obtained in the step (f) into an alkali liquor, stirring for 12-26 h at 60-90 ℃, and washing with deionized water until a washing liquid is neutral;
(h) drying the material obtained in the step (g);
or, further comprising:
(g) and (f) calcining the ball-milled material obtained in the step (f) in a muffle furnace at 450-650 ℃ for 2-5 hours.
Further, in the step (a), the organic solvent is ethanol.
Further, in the step (b), the stirred first solution was poured onto roll-to-roll blades to perform roll-to-roll coating, and the film thickness was 800 μm.
Further, in the step (c) and the step (d), the gradient temperature rise is performed independently in an oven at the corresponding temperature.
Furthermore, in the step (e), the inert gas is nitrogen, and the temperature rise rate of the calcination is 0.5-2 ℃/min.
Furthermore, in the step (g), the alkali solution is 2-5 mol/L potassium hydroxide aqueous solution.
Further, in the step (h), the temperature is kept at 80-100 ℃ for 12-16 hours.
Due to the application of the technical scheme, compared with the prior art, the invention has the following advantages: the method for mass production of the long-range ordered mesoporous carbon/mesoporous silicon material with ultrahigh specific surface area adopts the chemical products with stable yield and low price as raw materials, and has simple and easy processing steps, thereby greatly reducing the cost (to about two thousandth of the current selling price) and being beneficial to large-scale industrial application of the mesoporous material; more importantly, the prepared mesoporous carbon and mesoporous silicon materials have the advantages of long-range order, stable structure, uniform pore channels and large specific surface area, and can be used for multiple purposes of energy materials, adsorption materials and catalytic materials.
Drawings
FIG. 1 is a transmission electron microscope image of the ordered mesoporous material obtained in example 3.
Detailed Description
The invention relates to a mass production method of long-range ordered mesoporous carbon/mesoporous silicon material with ultrahigh specific surface area, which is characterized by comprising the following steps: coating, curing, pre-sintering, high-temperature sintering and crushing a raw material mixture containing phenolic resin, tetraethoxysilane and F127; when the product to be produced is mesoporous silicon carbon, performing ball milling to obtain particles; when the product to be produced is mesoporous carbon, ball-milling the mesoporous carbon to particles, soaking the particles in alkali liquor, heating and cleaning the particles; when the product to be produced in mass is mesoporous silicon, the mesoporous silicon is also ball-milled to particles and calcined in air or oxygen atmosphere. Chemical products with stable yield and low price are adopted as raw materials, and the process steps are simple and easy to implement, so that the cost can be greatly reduced, and the large-scale industrial application of mesoporous materials is facilitated; more importantly, the prepared mesoporous carbon and mesoporous silicon materials have the advantages of long-range order, stable structure, uniform pore channels and large specific surface area, and can be used for multiple purposes of energy materials, adsorption materials and catalytic materials.
The mass ratio of the phenolic resin to the tetraethoxysilane to the F127 is preferably 1: 2: under the proportion, the hydrophilic and hydrophobic groups in the components can form regularly arranged hexagonal stacked unit cells in the self-assembly process, so that a long-range ordered mesoporous structure can be obtained after sintering. Specifically, it comprises the following steps: (a) adding the phenolic resin, the tetraethoxysilane, the F127 and 0.1 mol/L hydrochloric acid into an organic solvent, and heating and stirring for 3-5 hours at 30-50 ℃ (the change of the stirring time in the range does not influence the product quality basically) to obtain a first solution; (b) coating the first solution by using a roll-to-roll technology, wherein the coating thickness is 200-1000 micrometers, and the optimal thickness is 800 micrometers; (c) carrying out gradient temperature rise on the film obtained in the step (b) within the temperature range of 40-60 ℃, and standing for 6-12 hours; (d) carrying out gradient temperature rise on the film obtained in the step (c) within a temperature range of 90-100 ℃, and standing for 6-12 hours; (e) calcining the film obtained in the step (d) at a high temperature of 750-850 ℃ for 3-5 hours in an inert gas atmosphere; (f) crushing the calcined material obtained in the step (e) to an average particle size of 2-3 mm, and ball-milling the crushed material to an average particle size of 1-10 μm; or, further comprising: (g) putting the ball-milling material obtained in the step (f) into an alkali liquor, stirring for 12-26 h at 60-90 ℃, and washing with deionized water until a washing liquid is neutral; (h) drying the material obtained in the step (g); or, further comprising: (g) calcining the ball-milled material obtained in the step (f) in a muffle furnace at 450-650 ℃ for 2-5 hours; although the invention is processed by a plurality of steps, each step is simple, easy to implement and free from harsh conditions, and is suitable for large-scale industrial application.
In the step (a), the organic solvent is ethanol; in the step (b), pouring the stirred first solution onto a roll-to-roll blade, and performing roll-to-roll film coating; in the step (c) and the step (d), the gradient temperature rise is carried out in the baking oven with corresponding temperature independently; in the step (e), the inert gas is nitrogen, and the temperature rising speed of calcination is 0.5-2 ℃/min; in the step (g), the alkali liquor is 2-5 mol/L potassium hydroxide aqueous solution; in the step (h), the temperature is kept at 80-100 ℃ for 12-16 hours, which is beneficial to ensuring and improving the specific surface area and the structure stability.
The following detailed description of preferred embodiments of the invention will be made.
Example 1
The embodiment provides a mass production method of a long-range ordered mesoporous carbon silicon material with ultrahigh specific surface area, which comprises the following steps:
(a) heating and stirring 500g of phenolic resin, 1000 g of ethyl orthosilicate, 500g of F127 and 10 ml of 0.1 mol/L hydrochloric acid in an ethanol solution at the temperature of 40 ℃ for 3-5 hours at room temperature;
(b) casting the stirred solution onto a blade of a roll-to-roll, and performing roll-to-roll film coating by using a PET substrate, wherein the coating speed is 1 cm/min, and the film thickness is 800 micrometers;
(c) allowing the film obtained in the step (b) to pass through a gradient oven at 40-60 ℃ by using roll-to-roll equipment, standing for 12 hours, wherein the length of the oven is 20 meters, and the temperature gradient is 1 ℃/meter;
(d) standing the film obtained in the step (c) in a temperature gradient oven at 90-100 ℃ for 12 hours in a roll-to-roll mode, wherein the length of the oven is 10 meters, and the temperature gradient is 1 ℃/meter;
(e) calcining the film obtained in the step (d) at high temperature, wherein the calcining temperature is 800 ℃, the calcining time is 3 hours, the calcining atmosphere is nitrogen, and the heating rate is 0.5 ℃/min;
(f) and (e) crushing the material obtained in the step (e) to an average particle size of 3mm, then placing the material in a ball milling tank, controlling the mass of a milling ball and the mass of the material to be 10:1, performing ball milling for 30 minutes at a rotation speed of 300 revolutions per minute until the average particle size is 5 mu m, and obtaining a final mesoporous carbon-silicon product.
Example 2
The present embodiment provides a mass production method of a long-range ordered mesoporous silicon material with ultrahigh specific surface area, which is basically the same as that in embodiment 1, except that: also comprises the following steps of (1) preparing,
(g) and (f) calcining the material obtained in the step (f) in a muffle furnace for 3 hours at the temperature of 550 ℃ to obtain a final mesoporous silicon product.
Example 3
The present embodiment provides a mass production method of a long-range ordered mesoporous carbon material with ultrahigh specific surface area, which is basically the same as that in embodiment 1, except that: also comprises the following steps of (1) preparing,
(g) putting the material obtained in the step (f) into a 3mol/L potassium hydroxide aqueous solution, heating to 60-90 ℃, stirring at a constant temperature for 12 hours, and cleaning the treated mesoporous carbon material with deionized water until the washing liquid is neutral;
(h) and (g) drying the mesoporous carbon material obtained in the step (g) in an oven at 90 ℃ for 12 hours to obtain a final mesoporous carbon product, wherein a scanning electron microscope picture of the final mesoporous carbon product is shown in figure 1.
Example 4
This example provides a mass production method of a long-range ordered mesoporous carbon material with ultrahigh specific surface area, which is basically the same as that in example 3, except that: the calcining temperature in the step (e) is 750 ℃, and the heating rate is 1 ℃/min.
Example 5
This example provides a mass production method of a long-range ordered mesoporous carbon material with ultrahigh specific surface area, which is basically the same as that in example 3, except that: the calcining temperature in the step (e) is 850 ℃, and the heating rate is 2 ℃/min.
Example 6
The present embodiment provides a mass production method of long-range ordered mesoporous carbon/mesoporous silicon material with ultra-high specific surface area, which is basically the same as that in embodiment 3, except that: in step (b), the coating film thickness was 200. mu.m.
Example 7
The present embodiment provides a mass production method of long-range ordered mesoporous carbon/mesoporous silicon material with ultra-high specific surface area, which is basically the same as that in embodiment 3, except that: in step (b), the coating film thickness was 1000. mu.m.
Comparative example 1
This example provides a mass production method of mesoporous carbon-silicon material, which is basically the same as that in example 1, except that: in step (a), no phenolic resin is used.
Comparative example 2
This example provides a mass production method of mesoporous carbon material, which is substantially the same as that in example 3, except that: in step (a), F127 was not used.
Comparative example 3
This example provides a mass production method of mesoporous carbon material, which is substantially the same as that in example 3, except that: step (c) was not performed.
Comparative example 4
This example provides a mass production method of mesoporous carbon material, which is substantially the same as that in example 3, except that: step (d) was not performed.
Comparative example 5
This example provides a mass production method of mesoporous carbon material, which is substantially the same as that in example 3, except that: the difference is that: in step (b), the coating film thickness was 2000. mu.m.
Comparative example 6
This example provides a mass production method of mesoporous carbon material, which is substantially the same as that in example 3, except that: the difference is that: in the step (a), the mass of the phenolic resin, the mass of the tetraethoxysilane and the mass of the F127 are respectively 500g, 5000g and 500 g.
Comparative example 7
This example provides a mass production method of mesoporous carbon material, which is substantially the same as that in example 3, except that: the difference is that: in the step (a), the mass of the phenolic resin, the mass of the tetraethoxysilane and the mass of the F127 are respectively 500g, 250g and 500 g.
Comparative example 8
This example provides a preparation method of a laboratory-grade mesoporous carbon material, which is substantially similar to the mass production method of the present application, and the specific differences are as follows: the mass of the phenolic resin, the weight of the tetraethoxysilane and the weight of the F127 added in the step (a) are respectively 1g, 2g and 1 g; the steps (b), (c) and (d) are not coated in a roll-to-roll manner, but are coated in a manner that the mixture is dropped on a glass dish.
Comparative example 9
This example provides a method for preparing a mesoporous carbon material, which is substantially the same as that in comparative example 8, except that: the weight of the raw materials is enlarged by 500 times.
The products of examples 1 to 7 and comparative examples 1 to 8 were tested, and the test data are shown in table 1.
TABLE 1 Performance Table of mesoporous carbon/mesoporous silicon/mesoporous carbon-silicon materials in examples 1-7 and comparative examples 1-8
Examples 1 to 3 show that mesoporous carbon silicon, mesoporous silicon, and mesoporous carbon having long-range order, stable structure, uniform pore channel, and large specific surface area can be prepared in mass production by using different process steps under the same precursor condition. The method combines the roll-to-roll process and the characteristic of evaporation-induced self-assembly, strictly controls the temperature of the product, can obtain the final product with high structural order degree in batches, and has remarkable progress. Comparing example 3 with comparative example 8, the performance of each aspect of the example 3 product can still be very close to that of comparative example 8 (a method commonly used in laboratories) under the condition that the yield of each batch of mass production product is 500 times that of the conventional laboratory product; the product of comparative example 9 was easily agglomerated into a lump, and a product of stable quality could not be obtained.
Examples 3 to 5 are control variables of temperature, and if the temperature rise speed is increased, the pores are excessively shrunk, so that the performance of the material is reduced, and even the ordered pore channel structure is damaged; under the temperature conditions of example 3 (800 ℃ C. and a temperature rise rate of 0.5 ℃/min), the final product has the most ordered structure (half-height width of first-order peak/lowest intensity of first-order peak) and the largest specific surface area.
Examples 6 and 7 are control variables for film thickness, and when the film reaches a selected thickness value (800 microns, example 3), the product properties will be intermediate between bulk and film; at thicknesses above 800 microns, the degree of order of the final product is significantly reduced (example 7); within 800 microns of thickness, the properties of the product are similar (example 6). This is because the effect of the coating thickness on the self-assembly performance comes from the interfacial effect of the PET substrate, and in the bulk, the self-assembly of the block copolymer is dragged by xyz 3 axes, so that the segment mobility is poor; in the film, however, the restriction in the z direction is small because the thickness is not large, and the movement of the segment is restricted only in the horizontal plane. Comparative example 5 is a control with respect to the change in coating film thickness, and when the coating film thickness reached 2000 μm, the product had properties more inclined to bulk than to thin film; in the bulk, the self-assembly conditions are more severe because the migration of the block copolymer segment is limited by the up-down, left-right, front-back 3 directions; at a thickness of 2000 microns, the resulting final product has no ordered structure.
Comparative example 1 is no added phenolic resin, in which case an ordered mesoporous structure can be formed, but the density of the final product would be greater than example 1 due to the absence of a silicon/carbon/oxygen triple self-assembled lattice structure, resulting in a smaller specific surface area than example 1. Comparative example 2 no F127 was added, in which case an ordered mesoporous structure could not be formed, and the final product had only micropores formed after potassium hydroxide had corroded silicon.
Comparative example 3 is a control group in which the solvent evaporation conditions were changed, and the film obtained was not subjected to solvent evaporation by roll-to-roll equipment through a gradient oven at 40 to 60 ℃ and directly subjected to subsequent heating. This can result in the block copolymer not having enough time to self-assemble to form a hexagonal packing unit cell structure and thus not forming an ordered channel structure.
Comparative example 4 control with respect to the change in the curing conditions of the polymer, standing for 12 hours without reel-to-reel in a temperature gradient oven at 90-100 ℃ resulted in: self-assembly cannot be further promoted to form long-range ordered cell structures because the gas during sintering destroys the structure of the incompletely cured cell walls, thereby affecting ordering.
Comparative examples 6 and 7 are control variables for carbon precursors, silicon precursors, and templating agents; if the proportion is not proper, the template agent cannot form a regularly arranged hexagonal cylindrical unit cell stacking structure, so that a long-range ordered pore channel structure cannot be formed; in comparative example 6, the mass ratio of the phenol resin, ethyl orthosilicate, and F127 was 0.5: 5: 0.5, the amount of template agent is far less than the critical micelle concentration requirement for forming the hexagonal cylindrical unit cell packing structure, so that in this case, the final product has no ordered mesoporous structure, and the specific surface area of the final product is mainly contributed by micropores formed by corroding silicon oxide by potassium hydroxide; comparative example 7, the mass ratio of the phenolic resin, ethyl orthosilicate and F127 is 2: 1: 2, at this ratio, the template can self-assemble into a lamellar structure, but after sintering, the structure collapses and does not form an ordered mesoporous structure, the specific surface area of which is also contributed by the micropores formed by the potassium hydroxide etching the silicon oxide.
Moreover, the product has the advantage that the cost of the existing mass production process is greatly reduced. Taking 300 kilograms of annual output as an example, the cost of the product is about 2.8 yuan/g, wherein the direct raw material cost (including electricity charge) is 0.8 yuan/g (industrial grade raw material), the equipment cost is 1.1 yuan/g (industrial grade equipment), the labor cost is 0.2 yuan/g, and the tax, environmental protection charge and miscellaneous charge are 0.7 yuan/g. Taking comparative example 8 as an example, the sale price is about 1500 yuan/g, the cost is about 970 yuan/g, wherein the direct raw material cost (including electricity charge) is 150 yuan/g (laboratory grade purity product), the equipment cost is 220 yuan/g (laboratory grade equipment), the labor cost is 400 yuan/g (daily output is about 3 g), and the cost of tax, environmental protection charge and miscellaneous charge is 200 yuan/g.
The above embodiments are merely illustrative of the technical ideas and features of the present invention, and the purpose thereof is to enable those skilled in the art to understand the contents of the present invention and implement the present invention, and not to limit the protection scope of the present invention. All equivalent changes and modifications made according to the spirit of the present invention should be covered within the protection scope of the present invention.
Claims (9)
1. A mass production method of long-range ordered mesoporous carbon/mesoporous silicon material with ultrahigh specific surface area is characterized in that: coating, curing, pre-sintering, high-temperature sintering and crushing a raw material mixture containing phenolic resin, tetraethoxysilane and F127;
when the product to be produced is mesoporous silicon carbon, performing ball milling to obtain particles;
when the product to be produced is mesoporous carbon, ball-milling the mesoporous carbon to particles, soaking the particles in alkali liquor, heating and cleaning the particles;
when the product to be produced in mass is mesoporous silicon, the mesoporous silicon is also ball-milled to particles and calcined in air or oxygen atmosphere.
2. The mass production method of the long-range ordered mesoporous carbon/mesoporous silicon material with ultrahigh specific surface area according to claim 1, wherein the mass production method comprises the following steps: the mass ratio of the phenolic resin to the tetraethoxysilane to the F127 is 1: 2: 1.
3. the method for mass production of the long-range ordered mesoporous carbon/mesoporous silicon material with ultrahigh specific surface area according to claim 1 or 2, comprising the following steps:
(a) adding the phenolic resin, the ethyl orthosilicate, the F127 and 0.1 mol/L hydrochloric acid into an organic solvent, and heating and stirring at 30-50 ℃ for 3-5 hours to obtain a first solution;
(b) coating the first solution with a film;
(c) carrying out gradient temperature rise on the film obtained in the step (b) within the temperature range of 40-60 ℃, and standing for 6-12 hours;
(d) carrying out gradient temperature rise on the film obtained in the step (c) within a temperature range of 90-100 ℃, and standing for 6-12 hours;
(e) calcining the film obtained in the step (d) at a high temperature of 750-850 ℃ for 3-5 hours in an inert gas atmosphere;
(f) crushing the calcined material obtained in the step (e) to an average particle size of 2-3 mm, and ball-milling to an average particle size of 1-10 mu m;
or, further comprising: (g) putting the ball-milling material obtained in the step (f) into an alkali liquor, stirring for 12-26 h at 60-90 ℃, and washing with deionized water until a washing liquid is neutral;
(h) drying the material obtained in the step (g);
or, further comprising:
(g) and (f) calcining the ball-milled material obtained in the step (f) in a muffle furnace at 450-650 ℃ for 2-5 hours.
4. The mass production method of the long-range ordered mesoporous carbon/mesoporous silicon material with ultrahigh specific surface area according to claim 3, wherein the mass production method comprises the following steps: in the step (a), the organic solvent is ethanol.
5. The mass production method of the long-range ordered mesoporous carbon/mesoporous silicon material with ultrahigh specific surface area according to claim 3, wherein the mass production method comprises the following steps: in the step (b), the stirred first solution is poured on a blade of a roll-to-roll film coating.
6. The mass production method of the long-range ordered mesoporous carbon/mesoporous silicon material with ultrahigh specific surface area according to claim 3, wherein the mass production method comprises the following steps: in the step (c) and the step (d), the gradient temperature rise is carried out in the ovens with corresponding temperatures independently.
7. The mass production method of the long-range ordered mesoporous carbon/mesoporous silicon material with ultrahigh specific surface area according to claim 3, wherein the mass production method comprises the following steps: in the step (e), the inert gas is nitrogen, and the temperature rise speed of the calcination is 0.5-2 ℃/min.
8. The mass production method of the long-range ordered mesoporous carbon/mesoporous silicon material with ultrahigh specific surface area according to claim 3, wherein the mass production method comprises the following steps: in the step (g), the alkali liquor is 2-5 mol/L potassium hydroxide aqueous solution.
9. The mass production method of the long-range ordered mesoporous carbon/mesoporous silicon material with ultrahigh specific surface area according to claim 3, wherein the mass production method comprises the following steps: in the step (h), the temperature is kept at 80-100 ℃ for 12-16 hours.
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