Mesoporous carbon material, method for preparing the same and use thereof
By combining high-viscosity slurry and surfactant, the difficulties in the large-scale production of mesoporous carbon materials using the EISA method have been overcome, achieving low-cost and high-efficiency preparation of mesoporous carbon materials with good stability and pore structure.
Patent Information
- Application Number
- CN202411970207.1
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2024-12-30
- Publication Date
- 2026-06-30
Smart Images
Figure CN122301183A_ABST
Abstract
Description
Technical Field
[0001] This invention belongs to the technical field of mesoporous carbon materials, and relates to a mesoporous carbon material, its preparation method, and its uses. Background Technology
[0002] Ordered mesoporous carbon materials, due to their unique physicochemical properties, show broad application prospects in various fields such as catalysis, energy storage and conversion, gas adsorption and separation, and biomedicine. These materials typically have pore sizes between 2 and 50 nanometers, possessing highly ordered pore structures, large specific surface areas, and good thermal and chemical stability. These properties not only promote efficient mass transport but also provide more anchoring sites for active components, thereby significantly improving performance in related applications.
[0003] Currently, the main methods for preparing ordered mesoporous carbon materials include hard template methods and soft template methods. Hard template methods use inorganic oxides such as silica as templates, allowing for precise control of pore size and shape. However, this process often requires complex synthesis steps and expensive template removal processes, limiting its application in large-scale production. In contrast, soft template methods utilize micelles formed from surfactants or polymers as templates, enabling the direct synthesis of highly ordered mesoporous materials under mild conditions, which are then converted into mesoporous carbon materials during subsequent high-temperature processing. This method is simple to operate and allows for easy control of the pore size distribution and morphology of the material, thus it is considered a more ideal synthetic strategy.
[0004] However, despite the numerous advantages that ordered mesoporous carbon materials prepared by the soft template method have shown in laboratory research, their industrial-scale application still faces several challenges. First, the reaction conditions of the soft template method significantly affect the quality of the final product; variations in factors such as temperature and pH can lead to inconsistencies in the material structure. Therefore, the persistent scale-up effect has prevented the soft template method from achieving large-scale production. Second, the surfactants used in the soft template method are expensive; if not recycled, this will result in persistently high product costs.
[0005] In common soft template methods, the hydrothermal method has been unable to scale up to 2m due to the unavoidable scale-up effect in aqueous solutions. 3 The above describes industrial-scale synthesis reactors. While evaporation-induced self-assembly (EISA) can be used for film preparation, it is also limited and cannot achieve large-scale production. Furthermore, the liquid raw materials used in EISA typically have a solids content of around 3%, resulting in low viscosity and inability to adhere to the film. Simultaneously, even if the raw material can adhere to the film, the resulting film thickness after drying will be too thin, making film demolding difficult. Moreover, excessively low solids content also necessitates the evaporation of large amounts of solvent, significantly increasing energy consumption and material costs in the production process.
[0006] Therefore, how to scale up the production of mesoporous carbon materials prepared by the EISA method and reduce the preparation cost is an urgent technical problem to be solved. Summary of the Invention
[0007] To address the shortcomings of existing technologies, the present invention aims to provide a mesoporous carbon material, its preparation method, and its applications. The preparation method provided by this invention, through the synergistic combination of a high-viscosity slurry and a surfactant extraction scheme, enables the large-scale production of mesoporous carbon materials prepared by the EISA method. Simultaneously, it effectively recovers the surfactant, avoiding waste of raw materials and reducing preparation costs. The method yields mesoporous carbon materials with a highly ordered pore structure, a large specific surface area, and good thermal and chemical stability.
[0008] To achieve this objective, the present invention employs the following technical solution:
[0009] In a first aspect, the present invention provides a method for preparing a mesoporous carbon material, the method comprising the following steps:
[0010] By mixing carbon source, solvent and surfactant, a slurry with a viscosity of 2.98×10^-3 Pa·s to 20 Pa·s was obtained;
[0011] The slurry was subjected to evaporation-induced self-assembly to obtain a mesoporous carbon precursor material.
[0012] Mesoporous carbon precursor materials are obtained by extracting surfactants and carbonizing them.
[0013] For example, the viscosity can be 2.98×10^-3 Pa·s, 1×10^-2 Pa·s, 5×10^-2 Pa·s, 1×10^-1 Pa·s, 0.5 Pa·s, 1 Pa·s, 2 Pa·s, 3 Pa·s, 4 Pa·s, 5 Pa·s, 6 Pa·s, 7 Pa·s, 8 Pa·s, 9 Pa·s, 10 Pa·s, 11 Pa·s, 12 Pa·s, 13 Pa·s, 14 Pa·s, 15 Pa·s, 16 Pa·s, 17 Pa·s, 18 Pa·s, 19 Pa·s, or 20 Pa·s, but is not limited to the listed values; other unlisted values within this range are also applicable.
[0014] The preparation method provided by this invention, through the synergistic combination of high-viscosity slurry and surfactant extraction scheme, enables the large-scale production of mesoporous carbon materials prepared by EISA method, while also effectively recovering the surfactant, avoiding waste of raw materials and reducing preparation costs; and produces mesoporous carbon materials with highly ordered pore structure, large specific surface area, and good thermal and chemical stability.
[0015] The following are preferred technical solutions of the present invention, but are not intended to limit the technical solutions provided by the present invention. The technical objectives and beneficial effects of the present invention can be better achieved and realized through the following preferred technical solutions.
[0016] Preferably, the carbon source accounts for 10% to 90% of the mass of the slurry, more preferably 30% to 60%, such as 10%, 20%, 30%, 35%, 40%, 45%, 50%, 55%, 60%, 70%, 80%, or 90%, but is not limited to the listed values; other unlisted values within this range are also applicable.
[0017] In this invention, it is further preferred that the carbon source accounts for 30% to 60% of the mass of the slurry, thereby better controlling the viscosity of the slurry without affecting the normal coating of the slurry.
[0018] Preferably, the surfactant in the slurry accounts for 0% to 50% by mass, excluding 0%, for example, 1%, 5%, 10%, 15%, 20%, 25%, 30%, 35%, 40%, 45%, or 50%, but is not limited to the listed values. Other unlisted values within this range are also applicable.
[0019] Preferably, the solvent accounts for 0% to 50% of the mass of the slurry, excluding 0%, for example, 1%, 5%, 10%, 15%, 20%, 25%, 30%, 35%, 40%, 45%, or 50%, but is not limited to the listed values. Other unlisted values within this range are also applicable.
[0020] Preferably, the mixed raw materials also include additives.
[0021] In this invention, the role of the additive is to adjust the pH of the slurry and promote the subsequent curing of the slurry.
[0022] Preferably, the mass percentage of the additive in the slurry is 0% to 10% and does not include 0%, for example, 0.5%, 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9% or 10%, etc., but is not limited to the listed values, and other unlisted values within this range are also applicable.
[0023] Preferably, the additive includes a pH adjuster, which includes any one or a combination of at least two of KOH, HCl, or ZnCl2.
[0024] Preferably, the slurry is subjected to film formation treatment, and then evaporation-induced self-assembly is performed.
[0025] In this invention, mesoporous carbon materials are prepared using the EISA method. The continuous film-forming device enables the expansion and continuous production of mesoporous carbon. The film structure obtained from the slurry is then subjected to evaporation-induced self-assembly treatment, which is more conducive to the self-assembly of the structure-directing agent into a stable and orderly template structure during continuous production, avoiding the problem of poor structural consistency between different batches caused by intermittent production.
[0026] Preferably, the evaporation-induced self-assembly includes sequential evaporation and curing processes.
[0027] Preferably, the evaporation temperature of the evaporation process is 10 to 120°C, such as 10°C, 20°C, 30°C, 40°C, 50°C, 60°C, 70°C, 80°C, 90°C, 100°C, 110°C, or 120°C, but is not limited to the listed values. Other unlisted values within this range are also applicable.
[0028] Preferably, the curing temperature of the curing treatment is 60 to 200°C, such as 60°C, 70°C, 80°C, 90°C, 100°C, 110°C, 120°C, 130°C, 140°C, 150°C, 160°C, 170°C, 180°C, 190°C, or 200°C, but it is not limited to the listed values. Other unlisted values within this range are also applicable.
[0029] Preferably, during the extraction process, the mass ratio of the mesoporous carbon precursor material to the extractant is (1-5):1, such as 1:1, 2:1, 3:1, 4:1 or 5:1, but it is not limited to the listed values. Other unlisted values within this range are also applicable.
[0030] In the extraction process of this invention, the mass ratio of the self-assembled mesoporous carbon precursor material membrane to the extractant is (1-5):1, which can achieve more thorough recovery of surfactant and avoid cost increase or precursor swelling due to excessive use of extractant, which would affect the properties of the precursor material.
[0031] Preferably, the extraction temperature is 0 to 100°C, such as 0°C, 10°C, 20°C, 30°C, 40°C, 50°C, 60°C, 70°C, 80°C, 90°C, or 100°C, but is not limited to the listed values. Other unlisted values within this range are also applicable.
[0032] Preferably, the carbonization temperature is 600 to 1000°C, such as 600°C, 700°C, 800°C, 900°C, or 1000°C, but is not limited to the listed values. Other unlisted values within this range are also applicable.
[0033] As a preferred technical solution, the preparation method includes the following steps:
[0034] By mixing carbon source, solvent, surfactant and pH adjuster, a slurry with a viscosity of 2.98×10^-3 Pa·s to 20 Pa·s was obtained;
[0035] The slurry is subjected to film formation treatment, and then evaporation-induced self-assembly is performed. Evaporation-induced self-assembly includes sequential evaporation treatment at 10-120°C and curing treatment at 60-200°C to obtain mesoporous carbon precursor material.
[0036] The mesoporous carbon precursor material and the extractant were extracted with surfactant at a mass ratio of (1-5):1, and then carbonized at 600-1000℃ to obtain the mesoporous carbon material.
[0037] The carbon source accounts for 30% to 60% of the mass of the slurry, the surfactant accounts for 0% to 50% of the mass of the slurry (excluding 0%), the solvent accounts for 0% to 50% of the mass of the slurry (excluding 0%), and the additives account for 0% to 10% of the mass of the slurry (excluding 0%).
[0038] It should be noted that, apart from the above-mentioned feature limitations, the preparation process of the mesoporous carbon materials in this invention is a conventional technical solution, and those skilled in the art can make adaptive selections and adjustments according to actual needs.
[0039] For example:
[0040] The carbon source includes, but is not limited to, at least one of the following compounds with a residual carbon content >30% and capable of polymerizing into a solid: phenolic resin, furfuryl alcohol, epoxy resin, etc.
[0041] The surfactants include, but are not limited to, at least one of surfactants with amphiphilic groups such as P123, F127, Triton X-100, and Brij56.
[0042] The solvents include, but are not limited to, water and / or ethanol.
[0043] The extractant includes, but is not limited to, at least one of strongly polar solvents such as methanol, ethanol, and acetone.
[0044] The extraction can be a single extraction or multiple extractions.
[0045] Furthermore, the present invention does not impose special limitations on the film-forming device. For example, it can be a continuous film-forming device with a continuous conveyor belt. The film-forming device can also be combined with an evaporation device and a curing device to obtain a production device for continuous evaporation-induced self-assembly, so as to better realize the large-scale production of mesoporous carbon materials prepared by the EISA method.
[0046] In a second aspect, the present invention provides a mesoporous carbon material, which is prepared by the preparation method described in the first aspect.
[0047] Preferably, the most probable pore size of the mesoporous carbon material is 2 to 50 nm, such as 2 nm, 5 nm, 10 nm, 15 nm, 20 nm, 25 nm, 30 nm, 35 nm, 40 nm, 45 nm or 50 nm, but it is not limited to the listed values. Other unlisted values within this range are also applicable.
[0048] It should be noted that the most probable pore size in this invention refers to the pore size corresponding to the peak value on the differential distribution curve of the pore size, which is the pore size with the highest probability of occurrence.
[0049] Preferably, the specific surface area of the mesoporous carbon material is 500–800 m². 2 / g, for example 500m 2 / g、550m 2 / g、600m 2 / g、650m 2 / g、700m 2 / g、750m 2 / g or 800m 2 / g, etc., but not limited to the listed values; other unlisted values within this range also apply.
[0050] Thirdly, the present invention also provides a use of the mesoporous carbon material as described in the second aspect, wherein the mesoporous carbon material is used in any one of energy storage, catalyst support, gas adsorption and separation, or biomedicine.
[0051] Compared with the prior art, the present invention has the following beneficial effects:
[0052] The preparation method provided by this invention, through the synergistic combination of high-viscosity slurry and surfactant extraction scheme, enables the large-scale production of mesoporous carbon materials prepared by EISA method, while also effectively recovering the surfactant, avoiding waste of raw materials and reducing preparation costs; and produces mesoporous carbon materials with highly ordered pore structure, large specific surface area, and good thermal and chemical stability. Attached Figure Description
[0053] Figure 1 This is a schematic diagram of the preparation apparatus provided for a specific embodiment of the present invention.
[0054] Among them, 1-slurry placement unit, 2-continuous conveyor belt, 3-evaporation unit, 4-solvent recovery unit, 5-curing unit, 6-membrane separation unit, 61-membrane separation roller, 62-membrane scraping device, and 7-material receiving unit. Detailed Implementation
[0055] The technical solution of the present invention will be further illustrated below through specific embodiments. Those skilled in the art should understand that the embodiments described are merely illustrative of the present invention and should not be construed as limiting the invention in any way.
[0056] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this application belongs; the terminology used herein is for the purpose of describing particular embodiments only and is not intended to limit this application; the terms “comprising” and “having” and any variations thereof in this application are intended to cover non-exclusive inclusion.
[0057] Exemplarily, the present invention provides an apparatus for preparing mesoporous carbon precursor materials by evaporation-induced self-assembly of slurry:
[0058] like Figure 1 As shown, the preparation apparatus includes:
[0059] The system includes a slurry placement unit 1, an evaporation unit 3, a solvent recovery unit 4, a curing unit 5, a continuous conveyor belt 2, a membrane separation unit 6, and a material receiving unit 7.
[0060] The slurry placement unit 1 is located above the conveying surface of the continuous conveyor belt 2 and is used to store the slurry of the mesoporous carbon precursor and to coat the slurry of the mesoporous carbon precursor onto the conveying surface of the continuous conveyor belt 2.
[0061] The continuous conveyor belt 2 is connected in sequence to the evaporation unit 3 and the curing unit 5;
[0062] The evaporation unit 3 is used to evaporate the solvent from the coated film conveyed by the continuous conveyor belt 2 to obtain a soft film;
[0063] The solvent recovery unit 4 is used to recover the solvent evaporated in the evaporation unit 3;
[0064] The curing unit 5 is used to cure the soft film obtained by the evaporation unit 3 to obtain a self-assembled mesoporous carbon precursor material film.
[0065] The membrane separation unit 6 is located at the end of the continuous conveyor belt 2. The membrane separation unit 6 is used to separate the self-assembled mesoporous carbon precursor material membrane obtained by the curing unit 5 from the continuous conveyor belt 2.
[0066] The membrane separation unit 6 includes a membrane separation roller 61, which is located at the end of the continuous conveyor belt 2; the membrane separation unit 6 also includes a membrane scraping device 62, which is used to scrape off the residual hard membrane on the continuous conveyor belt 2.
[0067] The material receiving unit 7 is used to receive the material separated by the membrane separation unit 6.
[0068] The slurries provided in the following examples and comparative examples were all prepared into mesoporous carbon precursor materials using the above-described preparation apparatus.
[0069] Example 1
[0070] This embodiment provides a method for preparing mesoporous carbon materials, the method being as follows:
[0071] A slurry with a viscosity of 1 Pa·s was prepared by mixing phenolic resin, solvent ethanol and surfactant P123 in a mass ratio of 40:30:30.
[0072] The slurry is subjected to a film-forming process to obtain a wet film structure. The wet film structure is then subjected to evaporation treatment at 80°C. During the evaporation process, the solvent evaporates, and the surfactant begins to self-assemble.
[0073] A soft film structure was obtained, and then the soft film structure was cured at 150°C to obtain a mesoporous carbon precursor material.
[0074] The obtained mesoporous carbon precursor material was extracted with methanol as a solvent, wherein the mass ratio of the self-assembled mesoporous carbon precursor material film to methanol was 3:1, and the extraction temperature was 50℃.
[0075] The extracted material was carbonized at 800°C in a nitrogen atmosphere to obtain the mesoporous carbon material.
[0076] Example 2
[0077] The difference between this embodiment and Embodiment 1 is that the viscosity of the slurry in this embodiment is 20 Pa·s;
[0078] The phenolic resin, solvent ethanol, and surfactant P123 are mixed in a mass ratio of 55:10:35.
[0079] The remaining preparation methods and parameters are consistent with those in Example 1.
[0080] Example 3
[0081] The difference between this embodiment and Embodiment 1 is that the viscosity of the slurry in this embodiment is 2.98 × 10⁻³ Pa·s;
[0082] The phenolic resin, solvent ethanol, and surfactant P123 are mixed in a mass ratio of 20:70:10.
[0083] The remaining preparation methods and parameters are consistent with those in Example 1.
[0084] Example 4
[0085] The difference between this embodiment and Embodiment 1 is that in this embodiment, the mass ratio of the self-assembled mesoporous carbon precursor material film to methanol is 5:1.
[0086] The remaining preparation methods and parameters are consistent with those in Example 1.
[0087] Example 5
[0088] The difference between this embodiment and Embodiment 1 is that in this embodiment, the mass ratio of the self-assembled mesoporous carbon precursor material film to methanol is 1:1.
[0089] The remaining preparation methods and parameters are consistent with those in Example 1.
[0090] Example 6
[0091] The difference between this embodiment and Example 1 is that the raw materials used in this embodiment are phenolic resin, solvent ethanol, surfactant P123 and auxiliary agent ZnCl2, with a corresponding mass ratio of 45:20:30:5, and the viscosity of the resulting slurry is 5 Pa·s.
[0092] The remaining preparation methods and parameters are consistent with those in Example 1.
[0093] Example 7
[0094] The difference between this embodiment and Embodiment 1 is that in this embodiment, the mass ratio of the self-assembled mesoporous carbon precursor material film to methanol is 0.5:1.
[0095] The remaining preparation methods and parameters are consistent with those in Example 1.
[0096] Example 8
[0097] The difference between this embodiment and Embodiment 1 is that in this embodiment, the mass ratio of the self-assembled mesoporous carbon precursor material film to methanol is 6:1.
[0098] The remaining preparation methods and parameters are consistent with those in Example 1.
[0099] Comparative Example 1
[0100] The difference between this embodiment and Embodiment 1 is that the viscosity of the slurry in this embodiment is 1×10^-3 Pa·s;
[0101] The phenolic resin, solvent ethanol, and surfactant P123 are mixed in a mass ratio of 3:95:2.
[0102] The remaining preparation methods and parameters are consistent with those in Example 1.
[0103] Comparative Example 2
[0104] The difference between this embodiment and Embodiment 1 is that the viscosity of the slurry in this embodiment is 25 Pa·s;
[0105] The phenolic resin, solvent ethanol, and surfactant P123 are mixed in a mass ratio of 59:5:36.
[0106] The remaining preparation methods and parameters are consistent with those in Example 1.
[0107] The mesoporous carbon materials prepared in Examples 1-8 and Comparative Examples 1-2 were tested for most probable pore size and specific surface area according to GB / T 19587-2004. The test conditions were as follows: the obtained porous carbon materials were degassed in a vacuum environment at 200℃ for 6 hours, and then transferred to a Micromeritics Tristar 3000 specific surface area analyzer for nitrogen adsorption-desorption testing at -196℃. The test results are shown in Table 1.
[0108] Table 1
[0109]
[0110]
[0111] In summary, the preparation method provided by this invention, through the synergistic combination of high-viscosity slurry and surfactant extraction scheme, enables the large-scale production of mesoporous carbon materials prepared by EISA, while also effectively recovering the surfactant, avoiding waste of raw materials and reducing preparation costs; and produces mesoporous carbon materials with highly ordered pore structure, large specific surface area, and good thermal and chemical stability.
[0112] The applicant declares that the above description is only a specific embodiment of the present invention, but the protection scope of the present invention is not limited thereto. Those skilled in the art should understand that any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope disclosed in the present invention fall within the protection and disclosure scope of the present invention.
Claims
1. A method for preparing a mesoporous carbon material, characterized in that, The preparation method includes the following steps: By mixing carbon source, solvent and surfactant, a slurry with a viscosity of 2.98×10^-3 Pa·s to 20 Pa·s was obtained; The slurry was subjected to evaporation-induced self-assembly to obtain a mesoporous carbon precursor material. Mesoporous carbon precursor materials are extracted with surfactants and then carbonized to obtain mesoporous carbon materials.
2. The preparation method according to claim 1, characterized in that, The carbon source accounts for 10% to 90% of the mass of the slurry, preferably 30% to 60%. Preferably, the surfactant accounts for 0% to 50% by mass in the slurry, but does not exceed 0%. Preferably, the solvent accounts for 0% to 50% of the mass of the slurry, but does not exceed 0%.
3. The preparation method according to claim 1 or 2, characterized in that, The mixed raw materials also include additives, which account for 0% to 10% of the mass of the slurry, but not exceeding 0%. Preferably, the additive includes a pH adjuster, which includes any one or a combination of at least two of KOH, HCl, or ZnCl2.
4. The preparation method according to claim 1, characterized in that, The slurry is subjected to film formation treatment, followed by evaporation to induce self-assembly; Preferably, the evaporation-induced self-assembly includes sequential evaporation treatment and curing treatment; Preferably, the evaporation temperature of the evaporation treatment is 10–120°C; Preferably, the curing temperature of the curing treatment is 60–200°C.
5. The preparation method according to claim 1, characterized in that, During the extraction process, the mass ratio of mesoporous carbon precursor material to extractant is (1-5):1; Preferably, the extraction temperature is 0–100°C.
6. The preparation method according to claim 1, characterized in that, The carbonization temperature is 600–1000°C.
7. The preparation method according to claim 1, characterized in that, The preparation method includes the following steps: By mixing carbon source, solvent, surfactant and pH adjuster, a slurry with a viscosity of 2.98×10^-3 Pa·s to 20 Pa·s was obtained; The slurry is subjected to film formation treatment, and then evaporation-induced self-assembly is performed. Evaporation-induced self-assembly includes sequential evaporation treatment at 10-120°C and curing treatment at 60-200°C to obtain mesoporous carbon precursor material. The mesoporous carbon precursor material and the extractant were extracted with surfactant at a mass ratio of (1-5):1, and then carbonized at 600-1000℃ to obtain the mesoporous carbon material. The carbon source accounts for 30% to 60% of the mass of the slurry, the surfactant accounts for 0% to 50% of the mass of the slurry (excluding 0%), the solvent accounts for 0% to 50% of the mass of the slurry (excluding 0%), and the additives account for 0% to 10% of the mass of the slurry (excluding 0%).
8. A mesoporous carbon material, characterized in that, The mesoporous carbon material is prepared by the preparation method according to any one of claims 1-7.
9. The mesoporous carbon material according to claim 8, characterized in that, The most probable pore size of the mesoporous carbon material is 2–50 nm; the specific surface area of the mesoporous carbon material is 500–800 m². 2 / g.
10. Use of a mesoporous carbon material as described in claim 8 or 9, characterized in that, The mesoporous carbon material can be used in any of the following applications: energy storage, catalyst support, gas adsorption and separation, or biomedicine.