CN116262611A - Preparation method of long-range ordered mesoporous carbon material with high boron content doping and high specific surface area - Google Patents
Preparation method of long-range ordered mesoporous carbon material with high boron content doping and high specific surface area Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/05—Preparation or purification of carbon not covered by groups C01B32/15, C01B32/20, C01B32/25, C01B32/30
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Abstract
The invention discloses a preparation method of a long-range ordered mesoporous carbon material with high boron content and high specific surface area, which comprises the steps of coating a raw material mixture containing phenolic resin, ethyl orthosilicate and F127 from reel to reel, solidifying, pre-firing, presintering and crushing to obtain precursor powder; mixing the powder with boric acid, pre-sintering, calcining, soaking in alkali liquor, and oven drying. The method adopts the chemical products with stable yield and low price as raw materials, and has simple and easy process steps, thereby greatly reducing the cost and being beneficial to the large-scale industrialized application of the boron-doped mesoporous carbon material.
Description
Technical Field
The invention belongs to the field of nano materials, relates to a mesoporous carbon material, and in particular relates to a preparation method of a long-range ordered mesoporous carbon material with high boron content and high specific surface area.
Background
The ordered nano porous carbon material has wide application prospect in the fields of super capacitor, hydrogen storage, carbon dioxide trapping, selective adsorption, medicine slow release and the like. Sp, among the carbon materials 2 ,sp 3 The presence of hybridization and combination of ordered pore channels enable the ordered mesoporous carbon material to have unique physicochemical characteristics, such as high conductivity, low density, high porosity, strong chemical durability and the like.
The doping of the hetero elements is an important way for adjusting the characteristics of the carbon material to meet the special application of the carbon material in different fields, and the performances of the material such as hardness, optical characteristics, heat resistance, radiation resistance, chemical resistance, electrical insulation, conductivity, surface and interface characteristics and the like can be microscopically adjusted by introducing the hetero elements to form a new hybridization orbit.
Boron doped mesoporous carbon is one of the hot spot research fields in doping. The boron atoms can form Sp in the carbon skeleton 2 The hybrid can form electron-deficient active centers, and has very wide application in the fields of lithium ion batteries, super capacitors, fuel cells and the like. Compared with a pure carbon skeleton structure, the boron-carbon polar bond can be formed by introducing heteroatom boron, so that the wettability of the electrode material and the polar electrolyte is increased, and the electrochemical activity, the cycle performance and the like of the material are greatly improved. Compared with a disordered pore structure, the boron doped ordered mesoporous carbon has larger specific surface area and a uniform pore structure, and is beneficial to rapid catalytic reaction. However, the current research focuses on how to realize efficient doping of boron and accurate characterization of doping species, and the morphology of boron-doped ordered mesoporous carbon can be controlled with less research; the morphology of the material often has an impact on its performance. Therefore, it is important to explore a simple preparation method of the boron doped ordered mesoporous carbon nanomaterial with controllable morphology.
At present, boron doped carbon materials mainly comprise an on-site doping method and a post-activation method. The on-site hybridization method is to utilize gasified carbon-containing organic matters and gasified boron-containing matters to grow to obtain boron-doped carbon materials after vapor deposition; this method requires expensive laboratory equipment, and the final product obtained per batch is very small, and can only meet the requirements of scientific research, but cannot meet the requirements of large-scale industrial production. The post-activation method refers to performing post-functionalization on the prepared carbon material in boron-containing activation gas (usually boron trichloride), and the reaction conditions are usually extremely high in temperature requirement, but the post-activation method is usually very high in energy consumption (high temperature is required), and the obtained boron doping content is usually very low (generally less than 1%), which is that the melting boiling point of the boron precursor is usually very low, and the boron precursor is difficult to be inserted into the carbon skeleton in the carbonization process. The boron-doped mesoporous carbon prepared by the current method for preparing the boron-doped mesoporous carbon has extremely low doping content (generally less than 2 percent), and has no method for flexibly changing the proportion of boron doping to adapt to different requirements. Therefore, a fast, efficient, stable, controllable, high proportion boron doped ordered mesoporous carbon solution is urgently needed for commercialization of boron doped mesoporous carbon.
Disclosure of Invention
Aiming at the defects in the prior art, the invention provides a preparation method of a long-range ordered mesoporous carbon material with high boron content and high specific surface area, so as to realize the mass production of the boron-doped carbon material with low cost.
The technical scheme adopted for solving the technical problems is as follows:
a method for producing a long-range ordered mesoporous carbon material with high boron content and high specific surface area comprises the steps of coating, solidifying, pre-firing, presintering and crushing a raw material mixture containing phenolic resin, tetraethoxysilane and F127 to obtain powder; mixing the powder with boric acid, calcining, soaking in alkali liquor, and oven drying.
Further, the mass ratio of the phenolic resin to the tetraethyl orthosilicate to the F127 to the boric acid is 1:2:1.
further, the mass ratio of the boric acid to the powder is 0.1-30: 1.
further, it comprises the steps of:
(a) Adding the phenolic resin, the tetraethoxysilane, the F127 and 0.1mol/L hydrochloric acid into an organic solvent, heating and stirring for 3-5 hours at 30-50 ℃ to obtain a first solution;
(b) Coating the first solution;
(c) Carrying out gradient heating on the film obtained in the step (b) in the temperature range of 40-60 ℃ and standing for 6-12 hours;
(d) Carrying out gradient heating on the film obtained in the step (c) in the temperature range of 90-100 ℃, and standing for 6-12 hours;
(e) Taking down the film obtained in the step (d), and presintering at 250-350 ℃;
(f) Crushing the presintered product obtained in the step (e), and mixing the crushed presintered product with boric acid according to a proportion to obtain a mixture;
(g) Calcining the mixture at 800-1000 ℃ in inert atmosphere for 3-5 hours;
(h) Placing the material obtained in the step (g) into alkali liquor, stirring for 12-26 h at 60-90 ℃, and washing with deionized water until the washing liquor is neutral;
(i) And (3) drying the material obtained in the step (h).
Still further, in step (a), the organic solvent is ethanol.
Further, in the step (b), the stirred first solution is poured onto the reel-to-reel blade to perform reel-to-reel film coating.
Still further, in step (c) and step (d), the gradient heating is performed independently of each other in an oven at the corresponding temperature.
Further, in the step (g), the inert gas is nitrogen, and the temperature rising speed of calcination is 0.5-2 ℃/min.
Further, in the step (h), the alkali liquor is a potassium hydroxide aqueous solution with the concentration of 2-5 mol/L.
Further, in the step (i), the temperature is 80-100 ℃ for 12-16 hours.
The preparation method of the long-range ordered mesoporous carbon material with high boron content and high specific surface area adopts chemicals with stable yield and low price as raw materials, has simple and easy process steps, can greatly reduce the cost, realizes the mass production of the boron-doped mesoporous carbon material, and is beneficial to large-scale industrialized application of the boron-doped mesoporous carbon material; more importantly, the prepared boron doped mesoporous carbon has long-range order, stable structure, uniform pore canal and large specific surface area, and the boron doping content is greatly higher than that of other similar materials, so that the boron doped mesoporous carbon can be used as an energy material, an adsorption material, a catalytic material and the like for various purposes.
Drawings
FIG. 1 is a transmission electron microscope image and an X-ray energy spectrum of a boron doped mesoporous carbon material of example 3;
FIG. 2 is an X-ray photoelectron spectrum of the boron doped mesoporous carbon material of example 3;
FIG. 3 is a small angle diffraction pattern of the boron doped mesoporous carbon material of example 3;
fig. 4 is a small angle diffraction pattern of the boron doped mesoporous carbon material of comparative example 1.
Detailed Description
The invention relates to a preparation method of a long-range ordered mesoporous carbon material with high boron content and high specific surface area, which comprises the steps of coating, solidifying, pre-firing, presintering and crushing a raw material mixture containing phenolic resin, tetraethoxysilane and F127 to obtain powder; mixing the powder with boric acid, calcining, soaking in alkali liquor, and oven drying. The chemical product with stable yield and low price is adopted as the raw material, and the process steps are simple and easy to implement, thereby greatly reducing the cost and being beneficial to the large-scale and industrialized application of the boron-doped mesoporous carbon material; the prepared boron doped mesoporous carbon has long-range order, stable structure, uniform pore canal and large specific surface area, and the boron doping content is greatly higher than that of other similar materials, so that the boron doped mesoporous carbon can be used for various purposes of energy materials, adsorption materials and catalytic materials.
The mass ratio of the phenolic resin to the tetraethoxysilane to the F127 to the boric acid is preferably 1:2:1, hydrophilic and hydrophobic groups in the components can form regularly arranged hexagonal stacked unit cells in the self-assembly process, and a long-range ordered mesoporous structure can be obtained after sintering. The mass ratio of the boric acid to the powder is 0.1-30: 1, preferably 1 to 30:1, a step of; the optimal value is 1-10: 1, in the mass ratio range, high boron doping amount (boron content is more than 10%) can be ensured, and the long-range ordered mesoporous structure can be well maintained.
Specifically, the preparation method comprises the following steps: (a) Adding the phenolic resin, the tetraethoxysilane, the F127 and 0.1mol/L hydrochloric acid into an organic solvent, heating and stirring for 3-5 hours at 30-50 ℃ to obtain a first solution; (b) coating the obtained first solution; (c) Carrying out gradient heating on the film obtained in the step (b) in the temperature range of 40-60 ℃ and standing for 6-12 hours; (d) Carrying out gradient heating on the film obtained in the step (c) in the temperature range of 90-100 ℃, and standing for 6-12 hours; (e) Taking down the film obtained in the step (d), and presintering at 250-350 ℃; (f) Crushing the presintered product obtained in the step (e), and mixing the crushed presintered product with boric acid according to a proportion to obtain a mixture; (g) Calcining the obtained mixture at 800-1000 ℃ in inert atmosphere for 3-5 hours; (h) Placing the material obtained in the step (g) into 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 operate and has no harsh condition, and is suitable for large-scale industrialized application, and the steps are matched cooperatively to obtain the high boron doped mesoporous carbon product with long-range order, stable structure, uniform pore canal and large specific surface area.
In the step (a), the organic solvent is ethanol; in the step (b), pouring the stirred first solution on a roll-to-roll blade, and performing roll-to-roll film coating; in the step (c) and the step (d), the gradient heating is performed in an 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 a potassium hydroxide aqueous solution with the concentration of 2-5 mol/L; in the step (i), the temperature is between 80 and 100 ℃ for 12 to 16 hours; these are all beneficial to ensuring and improving the specific surface area and the stability of the product.
The preferred embodiments of the present invention will be described in detail.
Example 1:
the embodiment provides a preparation method of a long-range ordered mesoporous carbon material with high boron content doping and high specific surface area, which comprises the following steps:
(a) At room temperature, heating and stirring phenolic resin, tetraethoxysilane, F127 and 0.1mol/L hydrochloric acid in ethanol solution for 3-5 hours, wherein the mass ratio is 1:2:1, the temperature is 40 ℃;
(b) Casting the stirred solution on a roll-to-roll blade, and carrying out roll-to-roll film coating by using a PET substrate, wherein the coating speed is 1 millimeter/min;
(c) Passing the film obtained in the step (b) through a gradient oven (gradient heating is carried out in 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) Passing the film obtained in the step (c) through a gradient oven (gradient heating is carried out 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 presintering at 250-350 ℃;
(f) Crushing the presintered product obtained in the step (e) according to the weight ratio of 0.1:1 and boric acid (namely, the mass ratio of the presintered product to the boric acid is 1:0.1) are stirred and mixed to obtain a mixture;
(g) Calcining the mixture at 800 ℃ in nitrogen atmosphere for 3-5 hours, 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 crushed material in a ball milling tank, controlling the mass of the grinding balls and the mass of the material to be 10:1, ball milling for 30 minutes at a rotation rate of 300 r/min, and ball milling to an average particle size of 5 mu m; then placing the mesoporous carbon material in 3mol/L potassium hydroxide aqueous solution, heating to 60-90 ℃ and stirring for 12 hours at constant temperature, and cleaning the treated mesoporous carbon material with deionized water until washing liquid is neutral;
(i) And (3) placing the mesoporous carbon material obtained in the step (h) in an oven to be dried at 90 ℃ for 12 hours, and obtaining the final boron-doped mesoporous carbon product.
Example 2:
the present example provides a method for preparing a long-range ordered mesoporous carbon material with high boron content doping and high specific surface area, which is basically the same as that in example 1, except that: in the step (f), the mass ratio of boric acid to the presintered product is 0.5:1.
example 3:
the present example provides a method for preparing a long-range ordered mesoporous carbon material with high boron content doping and high specific surface area, which is basically the same as that in example 1, except that: in the step (f), the mass ratio of boric acid to the presintered product is 1:1, a step of; the transmission electron microscope is shown in figure 1, and the material can be seen from the figure to comprise an ordered cylindrical pore canal structure, and the structure is regular.
Example 4:
the present example provides a method for preparing a long-range ordered mesoporous carbon material with high boron content doping and high specific surface area, which is basically the same as that in example 1, except that: in the step (f), the mass ratio of boric acid to the presintered product is 10:1.
example 5:
the present example provides a method for preparing a long-range ordered mesoporous carbon material with high boron content doping and high specific surface area, which is basically the same as that in example 1, except that: in the step (f), the mass ratio of boric acid 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 mesoporous carbon material properties table for examples 1 to 5
As can be seen from the table, as the mass ratio of boron-containing precursor to carbon precursor increases, the amount of boron in the resulting final product increases; when the mass ratio of the boron-containing precursor to the carbon precursor is more than 10, the boron content is about 14 percent, and the carbon precursor tends to be stable.
FIG. 3 is a small angle diffraction electron microscope of the boron doped ordered mesoporous carbon obtained in example 3, and the material has clear first-order diffraction peak and second-order diffraction peak, which indicate regular structural arrangement and long-range order; the ratio of the second-order peak to the first-order peak is 1.73, and the ratio is consistent with the cylindrical hexagonal stacking hole structure and the transmission electron microscope image. The small angle diffraction electron micrographs of the other examples of examples 1-5 are similar to those of FIG. 3, but the first order peak intensities differ from the half-width ratios, indicating different order. As shown in the data of table 1, the order of the mesoporous materials of examples 1 to 5 decreases with increasing boron atom content. This is because when boron atoms react with carbon walls having a continuous lattice structure, local pressure is generated during the formation of boron carbon bonds and the reaction of carbon oxygen bonds, the tunnel structure is impacted during the hybridization reaction, and the structural order is affected by local stress changes.
Table 1 contains crystals calculated from the small angle diffraction patternFace spacing. It can be seen that as the boron precursor: the carbon precursor has the advantages that the mass percentage of the carbon precursor is increased, the inter-plane distance of the carbon precursor has a slight tendency to increase, and the degree of hybridization reaction is different under different mass proportions, so that the expansion degree of the carbon skeleton is different; however, this change is not particularly remarkable, and the interplanar spacing is maintained around 10 nm. The specific surface area data (obtained from BET adsorption-desorption curves) of the boron-doped ordered mesoporous carbon obtained in examples 1 to 5 are shown in Table 1, and it can be seen that the prepared boron-doped mesoporous carbon has very large specific surface area (more than 1500m 2 /g); as the mass ratio of boron precursor to carbon precursor increases, the specific surface area gradually decreases, possibly due to the difference in the degree of hybridization reaction, which is caused by the difference in the reaction with the silicon skeleton in the hybridization reaction. When the boric acid content continues to rise, the macropore content in the carbon material continues to increase, probably due to the fact that under the condition of excessive dopant, the violent hybridization reaction tears the carbon wall, so that holes larger than the mesoporous scale are formed, and the ordered mesoporous structure is further destroyed. In the invention, the embodiment 3 maintains the long-range ordered pore canal structure while taking the high doping proportion (more than 8 percent) into consideration, and provides a plurality of possibilities for the application of the material in the fields of catalysis, energy storage and the like.
Example 6:
the present example provides a method for preparing a long-range ordered mesoporous carbon material with high boron content doping and high specific surface area, which is basically the same as that in example 3, except that: in step (c), the temperature gradient is 0.2 ℃/cm; in step (d), the temperature gradient was 0.05deg.C/cm.
Example 7:
the present example provides a method for preparing a long-range ordered mesoporous carbon material with high boron content doping and high specific surface area, which is basically the same as that in example 3, except that: in step (c), the temperature gradient is 0.2 ℃/cm; in step (d), the temperature gradient was 0.5 ℃ per cm.
Comparative example 1:
this example provides a method for preparing mesoporous carbon material, which is substantially identical to that in example 3, except that: in step (a), ethyl orthosilicate is not used.
Comparative example 2:
this example provides a method for preparing mesoporous carbon material, which is substantially identical to that in example 3, except that: in step (a), F127 is not used.
Comparative example 3:
this example provides a method for preparing mesoporous carbon material, which is substantially identical to that in example 3, except that: in the step (f), the addition amount of boric acid is too small, and the mass ratio of boric acid to the presintered product is 0.05:1.
comparative example 4:
this example provides a method for preparing mesoporous carbon material, which is substantially identical to that in example 3, except that: in the step (f), the boric acid is added in an excessive amount, and the mass ratio of the boric acid to the presintered product is 40:1.
comparative example 5:
this example provides a method for preparing mesoporous carbon material, which is substantially identical to 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 method for preparing mesoporous carbon material, which is substantially identical to 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 method for preparing mesoporous carbon material, which is substantially identical to that in example 3, except that: step (c) is not performed.
Comparative example 8:
this example provides a method for preparing mesoporous carbon material, which is substantially identical to that in example 3, except that: step (d) is not performed.
Comparative example 9:
this example provides a method for preparing mesoporous carbon material, which is different from that of example 3 in that the resin formed by boric acid and phenol is used in step (a) instead of phenolic resin, and no ethyl orthosilicate is added. There is no step (f) and no step (h).
Table 1 performance tables of mesoporous carbon materials obtained in examples 6 to 7, comparative examples 1 to 9
Examples 6 and 7 are control variables for film curing temperature conditions. The curing temperature affects the further formation of ordered self-assembled structures of the block copolymers, and the temperature gradient needs to be controlled within a suitable temperature interval. If the temperature gradient is too small, insufficient crosslinking may be caused, thereby degrading the order 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 phenomenon, and the properties of the product may be non-uniform to affect the structural order.
Comparative example 5 and comparative example 6 are control variables for carbon precursor, silicon precursor, template. If the proportion is not proper, the template agent cannot form a regular hexagonal column 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 phenolic resin, the tetraethyl orthosilicate and the F127 was 0.5:5:0.5, the amount of template agent is far less than the critical micelle concentration requirement for forming a hexagonal cylinder unit cell stacking structure, in which case the final product has no ordered mesoporous structure, and the specific surface area is mainly contributed by micropores formed by the corrosion of silicon oxide by potassium hydroxide; because no ordered mesoporous structure exists, the dopant cannot fully contact the carbon wall, so that the boron doping content is greatly reduced. Comparative example 6, the mass ratio of phenolic resin, tetraethyl orthosilicate, F127 is 2:1:2, under the proportion, the template agent can self-assemble into a lamellar structure, but after sintering, the structure collapses and an ordered mesoporous structure is not formed, the specific surface area of the template agent is contributed by micropores formed by the corrosion of silicon oxide by potassium hydroxide, and the boron doping content is greatly reduced.
Comparative example 1 is non-tetraethoxysilane, in which case an ordered mesoporous structure may be formed after the pre-sintering in step (e), but the mechanical properties of the ordered mesoporous walls are greatly reduced due to the lack of a triple self-assembled lattice structure of silicon/carbon/oxygen, resulting in complete destruction of the ordered mesoporous structure during the high temperature calcination in step (g). As shown in fig. 4, there is no first order peak in the small angle diffraction pattern symbolizing the long range order structure. This may be due to the hybridization reaction being highly exothermic and the material being shredded by the forces associated with gas generation.
Comparative example 2 was not added with F127, in which case an ordered mesoporous structure could not be formed, so that there was no mesopore to adsorb dopants by capillary effect and form sufficient contact with carbon wall, resulting in a great reduction in boron doping content.
Comparative examples 3 and 4 are control variables for the ratio of dopant to pre-sinter yield to mass. In comparative example 3, the very low dopant content resulted in a very low boron content of the final product. In comparative example 4, the dopant content was extremely high and the boron content of the final product was very high, but the first-order peak half-width/first-order peak strength reached 2.02, indicating that the ordered structure was destroyed to some extent. This may be caused by the destruction of a portion of the char wall when a vigorous hybridization reaction occurs.
Comparative example 7 is a control group with varying solvent evaporation conditions, and the resulting film was passed through a roll-to-roll apparatus to effect solvent evaporation without further subsequent heating in a gradient oven at 40-60 ℃. This results in the block copolymer not having enough time to self-assemble to form a hexagonal packed unit cell structure and thus not being able to form an ordered pore structure; meanwhile, in the high-temperature sintering step of the step (g), the hybridization reaction is that the order is continuously deteriorated.
Comparative example 8 is a control group with varying polymer curing conditions, which did not go through a roll-to-roll oven at a temperature gradient of 90-100 c for 12 hours resulted in: the self-assembly cannot be further promoted to form a long-range ordered pore structure, because the gas in the sintering process damages the structure of the pore walls which are not completely solidified, thereby affecting the ordering; meanwhile, in the high-temperature sintering step of the step (g), the hybridization reaction is that the order is continuously deteriorated.
Comparative example 9 is a control group (prepared with reference Microporous andMesopororousMaterials 142 (2011) 609-613) using the same boron doping reactant boric acid, but with boride in the precursor, from the literature. The boron doping level is very low (0.2%) compared to the product of the present application. This is because the process mechanism of the present invention is completely different from that in the literature. In the literature, a continuous carbon skeleton structure is formed firstly and then is doped later, and boron is difficult to be inserted into a formed continuous carbon network system as a hetero element. In the method, after ordered mesoporous polymer/silicon grid is formed, a boron source is added, and molten dopant is sucked into ordered pore channels by utilizing a mesoporous-scale capillary action mechanism, so that the dopant is fully contacted with the carbon wall, and the boron content of a final product is greatly increased. Along with the progress of the hybridization reaction, the boron source can be continuously supplemented by the principle of capillary action while being consumed, so that the full contact of boron and carbon molecules and the generation of compound bonds are ensured; and the proportion of the boron source can be adjusted, so that the boron content of the final product can be adjusted. After the tetraethoxysilane is added, the mechanical property of the formed carbon/silicon/oxygen grid structure is obviously enhanced compared with that of a pure carbon/oxygen grid 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 prior art is greatly reduced, the annual production of 300 kg is taken as an example, the cost of using the project is about 3.6 yuan/g, wherein the cost of direct raw materials (including electric charge) is 1.6 yuan/g (industrial grade raw materials), the equipment cost is 1.0 yuan/g (industrial grade equipment), the labor cost is 0.2 yuan/g, and the tax, the environmental protection fee and the parasitic fee are 0.8 yuan/g. Taking comparative example 9 as an example, the final product was disclosed to have a selling price of about 2700 yuan/g and a cost of about 1350 yuan/g, wherein the direct raw material cost (including electric charge) was 480 yuan/g (laboratory grade purity product), the equipment cost was 270 yuan/g (laboratory grade equipment), the labor cost was 400 yuan/g (daily yield of about 3 g), and the cost of tax, environmental protection fee, and parasitic fee was 200 yuan/g.
The technical conception and characteristics of the present invention are for those skilled in the art to understand the content of the present invention and implement the present invention accordingly, and the scope of the present invention is not limited thereto. Equivalent changes and modifications are intended to be included within the scope of the present invention.
Claims (8)
1. A preparation method of a long-range ordered mesoporous carbon material with high boron content doping and high specific surface area is characterized by comprising the following steps: coating, curing, pre-firing and pre-sintering a raw material mixture containing phenolic resin, tetraethoxysilane and F127 to obtain powder; mixing the powder with boric acid, calcining, soaking in alkali liquor, and oven drying;
the mass ratio of the phenolic resin to the tetraethyl orthosilicate to the F127 is 1:2:1, a step of;
the mass ratio of the boric acid to the powder is 0.5-30: 1.
2. the method for preparing the long-range ordered mesoporous carbon material with high boron content doping and high specific surface area as claimed in claim 1, which is characterized by comprising the following steps:
(a) Adding the phenolic resin, the tetraethoxysilane, the F127 and 0.1mol/L hydrochloric acid into an organic solvent, heating and stirring for 3-5 hours at the temperature of 30-50 ℃ to obtain a first solution;
(b) Coating the first solution;
(c) Carrying out gradient heating on the film obtained in the step (b) in the temperature range of 40-60 ℃ and standing for 6-12 hours;
(d) Carrying out gradient heating on the film obtained in the step (c) in the temperature range of 90-100 ℃, and standing for 6-12 hours;
(e) Taking down the film obtained in the step (d), and presintering at 250-350 ℃;
(f) Crushing the presintered product obtained in the step (e), and mixing the crushed presintered product with boric acid according to a proportion to obtain a mixture;
(g) Calcining the mixture at 800-1000 ℃ in inert atmosphere for 3-5 hours;
(h) Placing the material obtained in the step (g) into alkali liquor, stirring for 12-26 h at 60-90 ℃, and washing with deionized water until the washing liquor is neutral;
(i) And (3) drying the material obtained in the step (h).
3. The method for preparing the high-boron-content doped high-specific-surface-area long-range ordered mesoporous carbon material according to claim 2, which is characterized in that: in the step (a), the organic solvent is ethanol.
4. The method for preparing the high-boron-content doped high-specific-surface-area long-range ordered mesoporous carbon material according to claim 2, which is characterized in that: in the step (b), the stirred first solution is poured on the reel-to-reel blade, and reel-to-reel film coating is carried out.
5. The method for preparing the high-boron-content doped high-specific-surface-area long-range ordered mesoporous carbon material according to claim 2, which is characterized in that: in step (c) and step (d), the gradient heating is performed independently of each other in an oven at the corresponding temperature.
6. The method for preparing the high-boron-content doped high-specific-surface-area long-range ordered mesoporous carbon material according to claim 2, which is characterized in that: in the step (g), the inert gas is nitrogen, and the temperature rising speed of calcination is 0.5-2 ℃/min.
7. The method for preparing the high-boron-content doped high-specific-surface-area long-range ordered mesoporous carbon material according to claim 2, which is characterized in that: in the step (h), the alkali liquor is a potassium hydroxide aqueous solution with the concentration of 2-5 mol/L.
8. The method for preparing the high-boron-content doped high-specific-surface-area long-range ordered mesoporous carbon material according to claim 2, which is characterized in that: in step (i), the temperature is 80-100 ℃ for 12-16 hours.
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