CN111892035B - Mass production method of long-range ordered mesoporous carbon material with high nitrogen content and ultrahigh specific surface area - Google Patents
Mass production method of long-range ordered mesoporous carbon material with high nitrogen content and 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 material with high nitrogen content and ultrahigh specific surface area, which comprises the steps of coating, curing, pre-firing, pre-sintering and crushing a raw material mixture containing phenolic resin, tetraethoxysilane and F127 to obtain powder; mixing the powder with melamine, calcining, soaking in alkali liquor and drying. Chemical products with stable yield and low price are used 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 the nitrogen-doped mesoporous carbon material is facilitated.
Description
Technical Field
The invention belongs to the field of nano materials, relates to a mesoporous carbon material, and particularly relates to a mass production method of a long-range ordered mesoporous carbon material with high nitrogen content and ultrahigh specific surface area.
Background
In recent years, research and industrial application of carbon nanomaterials are actively conducted, and carbon nanomaterials, such as carbon nanotubes and graphene, are widely used in the fields of super-strong fibers, material reinforcements, hydrogen storage materials, lithium ion batteries, nanodevices, electronic devices, nanomachines, catalysis, etc., in view of their superior properties in terms of hardness, optical properties, heat resistance, radiation resistance, chemical resistance, electrical insulation, electrical conductivity, surface and interface properties, etc., as compared to other materials.
Among a plurality of nano carbon materials, the ordered mesoporous carbon material has wide application prospect in the fields of selective adsorption, drug slow release and the like due to the unique ordered pore channel structure and the huge surface area. After the doped hetero atoms are introduced into the active center, the doped hetero atoms can also be directly used as a catalyst, such as a cathode oxygen reduction catalyst of a fuel cell. Among them, the preparation and performance research of nitrogen-doped mesoporous carbon is one of the research hotspots in this field. Compared with the disordered pore structure, the nitrogen-doped ordered mesoporous carbon has larger specific surface area and unblocked pore channels, and is extremely favorable for the rapid progress of catalytic reaction. However, a great deal of research focuses on how to realize efficient nitrogen doping and accurate characterization of doping species, and the research on the shape controllable preparation of the nitrogen-doped ordered mesoporous carbon is less; and the morphology of the material tends to have an effect on its performance. Therefore, it is very important to explore a simple preparation method of the shape-controllable nitrogen-doped ordered mesoporous carbon nanomaterial.
At present, nitrogen-doped carbon materials mainly comprise an on-site doping method, a later-stage activation method and a direct carbonization method. The in-situ hybridization method is a nitrogen-doped carbon material obtained by growing gasified carbon-containing organic matters and gasified nitrogen-containing matters after meteorological deposition; the method needs expensive experimental instruments, and the number of final products obtained in each batch is very small, so that the method only can meet the requirements of scientific research and cannot meet large-scale industrial production. The post-activation method is to perform post-functionalization on the prepared carbon material in activated gas (usually ammonia gas) containing nitrogen, the reaction conditions usually have extremely high requirements on temperature, but the post-activation method usually has high energy consumption (high temperature is needed), and the obtained nitrogen doping content is usually very low (generally less than 5 percent), because stable carbon-carbon bonds need extremely high energy to break and form carbon-nitrogen bonds. The direct carbonization method is that organic micromolecules containing nitrogen are used as raw materials of a carbon precursor, and the carbon precursor containing nitrogen is generated and then carbonized; this method determines the final nitrogen content depending on the type of nitrogen precursor used, often with very low doping content (typically less than 10%), and there is no way to flexibly change the nitrogen doping ratio to suit different needs. Therefore, a scheme for rapidly, effectively, stably, controllably and proportionally mixing nitrogen with mesoporous carbon is urgently needed for realizing commercialization of the nitrogen-doped mesoporous carbon.
Disclosure of Invention
Aiming at the defects in the prior art, the invention provides a mass production method of a long-range ordered mesoporous carbon material with high nitrogen content and ultrahigh specific surface area.
The invention aims to provide a mass production method of a long-range ordered mesoporous carbon material with high nitrogen content and ultrahigh specific surface area, which comprises the steps of coating, curing, pre-firing, pre-sintering and crushing a raw material mixture containing phenolic resin, tetraethoxysilane and F127 to obtain powder; mixing the powder with melamine, calcining, soaking in alkali liquor and drying.
Optimally, the mass ratio of the phenolic resin to the tetraethoxysilane to the F127 to the melamine is 1: 2: 1.
optimally, the mass ratio of the melamine to the powder is 0.1-30: 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) taking down the film obtained in the step (d), and pre-sintering at 250-350 ℃;
(f) crushing the pre-sintered product obtained in the step (e), and mixing the crushed pre-sintered product with melamine according to a ratio to obtain a mixture;
(g) calcining the mixture at 800-1000 ℃ for 3-5 hours in an inert atmosphere;
(h) putting the material obtained in the step (g) into an alkali liquor, stirring for 12-26 h at 60-90 ℃, and washing with deionized water until the washing liquor is neutral;
(i) and (h) drying the material obtained in the step (h).
Further, in the step (a), the organic solvent is ethanol.
Further, in the step (b), the stirred first solution is poured onto a roll-to-roll blade to perform roll-to-roll coating.
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 (g), the inert gas is nitrogen, and the temperature rise rate of the calcination is 0.5-2 ℃/min.
Furthermore, in the step (h), the alkali liquor is 2-5 mol/L potassium hydroxide aqueous solution.
Further, in step (i), the temperature is kept at 80-100 ℃ for 12-16 hours.
The mass production method of the long-range ordered mesoporous carbon material with high nitrogen content and ultrahigh specific surface area adopts the chemical product with stable yield and low price as the raw material, 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 the nitrogen-doped mesoporous carbon material is facilitated; more importantly, the prepared nitrogen-doped mesoporous carbon has the advantages of long-range order, stable structure, uniform pore channel and large specific surface area, and the nitrogen doping content is greatly higher than that of other similar materials, so the nitrogen-doped mesoporous carbon can be used for multiple purposes of energy materials, adsorption materials and catalytic materials.
Drawings
FIG. 1 is a transmission electron micrograph and an X-ray energy spectrum of a mesoporous carbon material in example 3;
FIG. 2 is an X-ray photoelectron spectrum of a mesoporous carbon material of example 3;
FIG. 3 is a diffraction pattern at a small angle for a mesoporous carbon material of example 3;
fig. 4 is a diffraction pattern at a small angle for the mesoporous carbon material of comparative example 1.
Detailed Description
The invention relates to a mass production method of a long-range ordered mesoporous carbon material with high nitrogen content and ultrahigh specific surface area, which comprises the steps of coating, curing, pre-firing, pre-sintering and crushing a raw material mixture containing phenolic resin, tetraethoxysilane and F127 to obtain powder; mixing the powder with melamine, calcining, soaking in alkali liquor and drying. 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 the nitrogen-doped mesoporous carbon material is facilitated; more importantly, the prepared nitrogen-doped mesoporous carbon has the advantages of long-range order, stable structure, uniform pore channel and large specific surface area, and the nitrogen doping content is greatly higher than that of other similar materials, so the nitrogen-doped mesoporous carbon can be used for multiple purposes of energy materials, adsorption materials and catalytic materials.
The mass ratio of the phenolic resin, the tetraethoxysilane, the F127 and the melamine 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. The mass ratio of the melamine to the powder is 0.1-30: 1, preferably 1 to 30: 1; the optimal value is 1-10: 1, in the mass ratio range, the high nitrogen doping amount (nitrogen content is more than 10 percent) can be ensured, and the long-range ordered mesoporous structure can be well maintained.
Specifically, 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) taking down the film obtained in the step (d), and pre-sintering at 250-350 ℃; (f) crushing the pre-sintered product obtained in the step (e), and mixing the crushed pre-sintered product with melamine according to a ratio to obtain a mixture; (g) calcining the mixture at 800-1000 ℃ for 3-5 hours in an inert atmosphere; (h) putting the material obtained in the step (g) into an alkali liquor, stirring for 12-26 h at 60-90 ℃, and washing with deionized water until the washing liquor is neutral; (i) drying the material obtained in the step (h); although the invention is processed by the steps, each step is simple, easy to implement and free of harsh conditions, and is suitable for large-scale industrial application, and the steps are cooperatively matched to obtain the high-nitrogen doped mesoporous carbon, which has long-range order, stable structure, uniform pore channel and large specific surface area.
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 (g), the inert gas is nitrogen, and the temperature rising speed of calcination is 0.5-2 ℃/min; in the step (h), the alkali liquor is 2-5 mol/L potassium hydroxide aqueous solution; in the step (i), the temperature is kept at 80-100 ℃ for 12-16 hours; these are all beneficial to ensure and improve the specific surface area and stability of the product.
The following provides a detailed description of preferred embodiments of the invention.
Example 1
The embodiment provides a mass production method of a long-range ordered mesoporous carbon material with high nitrogen content and ultrahigh specific surface area, which comprises the following steps:
(a) heating and stirring phenolic resin, tetraethoxysilane, F127 and 0.1 mol/L hydrochloric acid in an ethanol solution at room temperature for 3-5 hours, wherein the mass ratio is 1: 2: 1, the temperature is 40 ℃;
(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 at a coating speed of 1 mm/min;
(c) enabling the film obtained in the step (b) to pass through a gradient oven (carrying out gradient heating within the range of 40-60 ℃) at 40-60 ℃ by using roll-to-roll equipment, and standing for 6-12 hours, wherein the temperature gradient is 0.1 ℃/cm;
(d) enabling the film obtained in the step (c) to pass through a gradient oven (carrying out gradient heating within the range of 90-100 ℃) at 90-100 ℃ by using roll-to-roll equipment, and standing for 6-12 hours, wherein the temperature gradient is 0.1 ℃/cm;
(e) taking down the film obtained in the step (d), and pre-sintering at 250-350 ℃;
(f) crushing the pre-sintered product obtained in the step (e) according to the weight ratio of 0.1: 1 and melamine (namely the mass ratio of the presintered product to the melamine is 1: 0.1) are stirred and mixed to obtain a mixture;
(g) calcining the mixture at 800 ℃ for 3-5 hours in a nitrogen atmosphere, wherein the heating rate is 0.5 ℃/min;
(h) crushing the material obtained in the step (g) to an average particle size of 3mm, then placing the material in a ball milling tank, controlling the mass of milling balls and the mass of the material to be 10:1, and carrying out ball milling for 30 minutes at a rotation speed of 300 revolutions per minute until the average particle size is 5 mu m; then placing the mesoporous carbon material in 3mol/L potassium hydroxide aqueous solution, heating to 60-90 ℃, stirring at constant temperature for 12 hours, and cleaning the treated mesoporous carbon material with deionized water until the washing liquid is neutral;
(i) and (h) drying the mesoporous carbon material obtained in the step (h) in an oven at 90 ℃ for 12 hours to obtain a final nitrogen-doped mesoporous carbon product.
Example 2
The present embodiment provides a mass production method of a long-range ordered mesoporous carbon material with high nitrogen content and ultra-high specific surface area, which is basically the same as that in embodiment 1, except that: in the step (f), the mass ratio of melamine to the presintered product is 0.5: 1.
example 3
The present embodiment provides a mass production method of a long-range ordered mesoporous carbon material with high nitrogen content and ultra-high specific surface area, which is basically the same as that in embodiment 1, except that: in the step (f), the mass ratio of melamine to the presintered product is 1: 1; the transmission electron microscope is shown in figure 1, and the material can be seen from the figure to comprise an ordered cylindrical pore channel structure, and the structure arrangement is regular.
Example 4
The present embodiment provides a mass production method of a long-range ordered mesoporous carbon material with high nitrogen content and ultra-high specific surface area, which is basically the same as that in embodiment 1, except that: in the step (f), the mass ratio of melamine to the presintered product is 10: 1.
example 5
The present embodiment provides a mass production method of a long-range ordered mesoporous carbon material with high nitrogen content and ultra-high specific surface area, which is basically the same as that in embodiment 1, except that: in the step (f), the mass ratio of melamine to the presintered product is 30: 1.
the mesoporous carbon materials of examples 1 to 5 were subjected to various performance tests, and the results are shown in table 1.
Table 1 table of properties of mesoporous carbon materials in examples 1 to 5
As can be seen from the table, as the mass ratio of the nitrogen-containing precursor to the carbon precursor increases, the nitrogen content in the resulting final product increases; when the mass ratio of the nitrogen-containing precursor to the carbon precursor is less than 1, the influence of the nitrogen content changing along with the nitrogen-containing precursor is large; when the mass ratio of the nitrogen-containing precursor to the carbon precursor is more than 1, the nitrogen content is about 20-25%, and the nitrogen tends to be stable.
FIG. 3 is a small-angle diffraction electron microscope image of the nitrogen-doped ordered mesoporous carbon obtained in example 3, and it can be seen from the image that the material has clear first-order and second-order diffraction peaks, indicating regular structural arrangement and long-range order; the crystal face spacing ratio of the second-order peak to the first-order peak is 1.73, and the crystal face spacing ratio is consistent with the structure of a cylindrical hexagonal stacking hole and the result of a transmission electron microscope image. The low angle diffraction electron micrographs of examples 1 to 5 are similar to those of FIG. 3, but the first order peak intensity differs from the full width at half maximum ratio, indicating a different ordering. As shown in the data of table 1, the degree of order of the mesoporous materials of examples 1 to 5 decreases with increasing nitrogen atom content. This is because the ordering of the structure is affected as the nitrogen atoms undergo a hybridization reaction with the carbon wall having a continuous lattice structure.
Table 1 contains the interplanar spacings calculated from the small angle diffractograms. It can be seen that with the nitrogen precursor: the increase of the mass percentage of the carbon precursor tends to slightly increase the interplanar spacing, which is probably caused by different degrees of expansion and expansion of the carbon skeleton due to different degrees of hybridization reaction under different mass ratios; this change is not particularly significant and the interplanar spacing remains around 10 nm. Table 1 contains the specific surface area data (obtained from BET adsorption-desorption curves) of the nitrogen-doped ordered mesoporous carbons obtained in examples 1 to 5, and it can be seen that the prepared nitrogen-doped mesoporous carbons all have very large specific surface areas (greater than 1500m 2/g); the specific surface area gradually decreases with the increase of the mass ratio of the nitrogen precursor to the carbon precursor, which may be caused by the difference of the degree of the hybridization reaction and the reaction with the silicon skeleton in the hybridization reaction. When the content of melamine is increased continuously, the content of macropores in the carbon material is increased continuously, which is probably because in the case of excessive dopants, the carbon wall is torn by violent hybridization reaction, so that pores larger than the mesoporous scale are formed, and the ordered mesoporous structure is further damaged.
Example 6
The present embodiment provides a mass production method of a long-range ordered mesoporous carbon material with high nitrogen content and ultra-high specific surface area, which is basically the same as that in embodiment 3, except that: in the step (c), the temperature gradient is 0.2 ℃/cm; in step (d), the temperature gradient is 0.05 ℃/cm.
Example 7
The present embodiment provides a mass production method of a long-range ordered mesoporous carbon material with high nitrogen content and ultra-high specific surface area, which is basically the same as that in embodiment 3, except that: in the step (c), the temperature gradient is 0.2 ℃/cm; in step (d), the temperature gradient is 0.5 ℃/cm.
Comparative example 1
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), no ethyl orthosilicate 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: in the step (f), the addition amount of melamine is too small, and the mass ratio of the melamine to the pre-sintered product is 0.05: 1.
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: in the step (f), the addition amount of melamine is too much, and the mass ratio of melamine to the pre-sintered product is 40: 1.
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 mass ratio of the phenolic resin to the tetraethoxysilane to the F127 is 0.5: 5: 0.5.
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 mass ratio of the phenolic resin to the tetraethoxysilane to the F127 is 2: 1: 2.
comparative example 7
This example provides a mass production method of mesoporous carbon material, which is basically the same as that in example 3, except that: step (c) was not performed.
Comparative example 8
This example provides a mass production method of mesoporous carbon material, which is basically the same as that in example 3, except that: step (d) was not performed.
Comparative example 9
This example provides a mass production method of mesoporous carbon material, which is different from example 3 in that a resin formed by melamine and phenol is used instead of phenol resin in step (a), and tetraethoxysilane is not added. There is no step (f) and no step (h).
Table 1 table of properties of mesoporous carbon materials in examples 6 to 7 and comparative examples 1 to 9
Examples 6 and 7 are control variables for film curing temperature conditions. The curing temperature can influence the block copolymer to further form an ordered self-assembled structure, and the temperature gradient needs to be controlled within a proper temperature interval. If the temperature gradient is too small, insufficient crosslinking may result, leading to reduced ordering of the final product; as shown in example 7, if the temperature gradient is too large, the stress of the heated film may be too large to cause cracking, and the properties of the product may be non-uniform, which may affect the order of the structure.
Comparative examples 5 and 6 are control variables for carbon precursor, silicon precursor, templating agent. 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 5, 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; due to the absence of the ordered mesoporous structure, the dopant cannot fully contact the carbon wall, so that the nitrogen doping content is greatly reduced. Comparative example 6, the mass ratio of the phenolic resin, ethyl orthosilicate, F127 was 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 the template is also contributed by micropores formed by the potassium hydroxide corroding silicon oxide, and the nitrogen doping content is greatly reduced.
Comparative example 1 is not tetraethoxysilane, in which case an ordered mesoporous structure can be formed after the pre-sintering of step (e), but the mechanical properties of the walls of the ordered mesoporous pores are greatly reduced due to the absence of a triple self-assembled lattice structure of silicon/carbon/oxygen, which results in complete destruction of the ordered mesoporous structure during the high-temperature calcination of step (g). As shown in fig. 4, there is no first order peak in the low angle diffractogram that would symbolize a long range order structure. This may be due to the force generated by the extensive exotherm of the hybridization reaction with concomitant gas generation tearing the material apart.
Comparative example 2F 127 was not added, and in this case, an ordered mesoporous structure could not be formed, and thus there was no mesopore to adsorb the dopant by capillary effect and to form sufficient contact with the carbon wall, resulting in a great reduction in the nitrogen doping content.
Comparative examples 3 and 4 are control variables for the dopant to presintering yield to mass ratio. In comparative example 3, the very low dopant level results in a very low nitrogen content in the final product. In comparative example 4, the dopant content was extremely high, and the nitrogen content of the final product was very high, but the full width at half maximum of the first-order peak/first-order peak intensity reached 0.9, indicating that the ordered structure was destroyed to some extent. This may be caused by the destruction of part of the carbon wall when a vigorous hybridization reaction occurs.
Comparative example 7 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 in a gradient oven at 40 to 60 ℃ and directly subjected to subsequent heating. This results in the block copolymer not having enough time to self-assemble into a hexagonal packing unit cell structure and thus not forming an ordered channel structure; meanwhile, in the high-temperature sintering step of step (g), the hybridization reaction is such that the order continues to deteriorate.
Comparative example 8 is a control of polymer curing conditions change, which did not result in 12 hours of roll-to-roll standing in a temperature gradient oven at 90-100 ℃: self-assembly cannot be further promoted to form a long-range ordered pore structure, because the gas in the sintering process destroys the structure of the incompletely cured pore wall, thereby affecting the ordering; meanwhile, in the high-temperature sintering step of step (g), the hybridization reaction is such that the order continues to deteriorate.
Comparative example 9 is a control (prepared with reference to j.phys. chem.c,2014,118, 2507-2517) using the same nitrogen-doped reactant melamine, but with nitridation in the precursor. Compared with the product of the application, the nitrogen doping content is low (5.46%), and no method is available for controlling the nitrogen doping content. This is because the proportion of nitrogen is fixed among precursors and cannot be adjusted; meanwhile, nitrogen in the precursor is easy to escape in the carbonization process, and no redundant nitrogen source can be supplemented, so that the final product is low in nitrogen doping content; in addition, the product obtains disordered mesoporous carbon. In the application, a nitrogen source is added after the ordered mesoporous polymer/silicon grid is formed, and the dopant is fully contacted with the carbon wall through the capillary action of the mesopores on the molten dopant, so that the nitrogen content of a final product is greatly increased; and the nitrogen content of the final product can be adjusted because the proportion of the nitrogen source can be adjusted. After the tetraethoxysilane is added, the formed carbon/silicon/oxygen latticed structure has stronger mechanical property compared with a pure carbon/oxygen latticed structure, so that the ordered mesoporous structure can be maintained in the hybridization reaction process.
The product has the advantages that the cost of the existing process is greatly reduced, for example, 300 kilograms of annual output is taken, the cost for using the project is about 3.0 yuan/g, wherein the cost of direct raw materials (including electricity charge) is 1.0 yuan/g (industrial raw materials), the cost of equipment is 1.1 yuan/g (industrial equipment), the labor cost is 0.2 yuan/g, and the tax, the environmental protection charge and the miscellaneous charge are 0.7 yuan/g. Taking comparative example 9 as an example, the final product is sold openly at a price of about 1800 Yuan/g and at a cost of about 1050 Yuan/g, wherein the direct raw material cost (including electricity charge) is 230 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 costs of tax, environmental protection charge and miscellaneous charge are 200 Yuan/g.
The technical idea and features of the present invention are intended to be understood and implemented by those skilled in the art, and the scope of the present invention is not limited thereby. 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 (7)
1. A mass production method of a long-range ordered mesoporous carbon material with high nitrogen content and ultrahigh specific surface area is characterized by comprising the following steps: coating, curing, pre-firing, pre-sintering and crushing a raw material mixture containing phenolic resin, tetraethoxysilane and F127 to obtain powder; mixing the powder with melamine, calcining, soaking in alkali liquor and drying; the mass ratio of the phenolic resin to the tetraethoxysilane to the F127 is 1: 2: 1; the mass ratio of the melamine to the powder is 1: 1 or 10-30: 1;
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) taking down the film obtained in the step (d), and pre-sintering at 250-350 ℃;
(f) crushing the pre-sintered product obtained in the step (e), and mixing the crushed pre-sintered product with melamine according to a ratio to obtain a mixture;
(g) calcining the mixture at 800-1000 ℃ for 3-5 hours in an inert atmosphere;
(h) putting the material obtained in the step (g) into an alkali liquor, stirring for 12-26 h at 60-90 ℃, and washing with deionized water until the washing liquor is neutral;
(i) and (h) drying the material obtained in the step (h).
2. The mass production method of the long-range ordered mesoporous carbon material with high nitrogen content and ultrahigh specific surface area according to claim 1, wherein the mass production method comprises the following steps: in the step (a), the organic solvent is ethanol.
3. The mass production method of the long-range ordered mesoporous carbon material with high nitrogen content and ultrahigh specific surface area according to claim 1, 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.
4. The mass production method of the long-range ordered mesoporous carbon material with high nitrogen content and ultrahigh specific surface area according to claim 1, 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.
5. The mass production method of the long-range ordered mesoporous carbon material with high nitrogen content and ultrahigh specific surface area according to claim 1, wherein the mass production method comprises the following steps: in the step (g), the inert atmosphere is a nitrogen atmosphere, and the temperature rise speed of the calcination is 0.5-2 ℃/min.
6. The mass production method of the long-range ordered mesoporous carbon material with high nitrogen content and ultrahigh specific surface area according to claim 1, wherein the mass production method comprises the following steps: in the step (h), the alkali liquor is 2-5 mol/L potassium hydroxide aqueous solution.
7. The mass production method of the long-range ordered mesoporous carbon material with high nitrogen content and ultrahigh specific surface area according to claim 1, wherein the mass production method comprises the following steps: in the step (i), the temperature is kept at 80-100 ℃ for 12-16 hours.
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