CN115650204A - Preparation method of hollow porous bowl-shaped carbon material - Google Patents
Preparation method of hollow porous bowl-shaped carbon material Download PDFInfo
- Publication number
- CN115650204A CN115650204A CN202211308195.7A CN202211308195A CN115650204A CN 115650204 A CN115650204 A CN 115650204A CN 202211308195 A CN202211308195 A CN 202211308195A CN 115650204 A CN115650204 A CN 115650204A
- Authority
- CN
- China
- Prior art keywords
- carbon material
- hollow porous
- aqueous solution
- shaped carbon
- porous bowl
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000003575 carbonaceous material Substances 0.000 title claims abstract description 32
- 238000002360 preparation method Methods 0.000 title claims abstract description 8
- 239000007864 aqueous solution Substances 0.000 claims abstract description 34
- -1 2,4-dicarbonylbenzoic acid Chemical compound 0.000 claims abstract description 16
- BCKXLBQYZLBQEK-KVVVOXFISA-M Sodium oleate Chemical compound [Na+].CCCCCCCC\C=C/CCCCCCCC([O-])=O BCKXLBQYZLBQEK-KVVVOXFISA-M 0.000 claims abstract description 15
- 238000010438 heat treatment Methods 0.000 claims abstract description 4
- 238000006243 chemical reaction Methods 0.000 claims description 21
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 claims description 12
- 239000000203 mixture Substances 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 9
- 238000002156 mixing Methods 0.000 claims description 8
- 238000005406 washing Methods 0.000 claims description 6
- 239000011259 mixed solution Substances 0.000 claims description 5
- 239000000243 solution Substances 0.000 claims description 5
- 238000001816 cooling Methods 0.000 claims description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 2
- 238000000926 separation method Methods 0.000 claims description 2
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 claims description 2
- 238000009210 therapy by ultrasound Methods 0.000 claims description 2
- 238000001291 vacuum drying Methods 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 4
- 238000000034 method Methods 0.000 abstract description 12
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 4
- 229910052799 carbon Inorganic materials 0.000 abstract description 4
- 239000004094 surface-active agent Substances 0.000 abstract description 3
- 239000007833 carbon precursor Substances 0.000 abstract description 2
- 239000011148 porous material Substances 0.000 abstract description 2
- 238000001179 sorption measurement Methods 0.000 abstract description 2
- 238000006555 catalytic reaction Methods 0.000 abstract 1
- 239000003814 drug Substances 0.000 abstract 1
- 239000000126 substance Substances 0.000 description 18
- 239000000463 material Substances 0.000 description 7
- 238000001035 drying Methods 0.000 description 4
- 238000002604 ultrasonography Methods 0.000 description 3
- 235000010299 hexamethylene tetramine Nutrition 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 238000003917 TEM image Methods 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000011258 core-shell material Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000012621 metal-organic framework Substances 0.000 description 1
- 125000001434 methanylylidene group Chemical group [H]C#[*] 0.000 description 1
- 239000000693 micelle Substances 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- 238000007039 two-step reaction Methods 0.000 description 1
- 239000013153 zeolitic imidazolate framework Substances 0.000 description 1
Images
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/13—Energy storage using capacitors
Landscapes
- Carbon And Carbon Compounds (AREA)
Abstract
The invention discloses a preparation method of a porous bowl-shaped carbon material, which takes 2,4-dicarbonylbenzoic acid as a carbon source and sodium oleate as a surfactant, and reduces a carbon precursor into a porous bowl-shaped structure with a regular shape and a uniform size by adopting an aqueous solution heating method. The porous bowl-shaped carbon material prepared by the invention has potential application prospects in the aspects of catalysis, adsorption, medicine, environment and the like due to the unique shape, the special pore structure, good conductivity and the like.
Description
Technical Field
The invention belongs to the technical field of catalyst preparation, and particularly relates to a preparation method of a hollow porous bowl-shaped carbon material.
Background
The hollow porous bowl-shaped carbon material integrates the advantages of carbon-based materials, a unique hollow porous structure and the like, and is widely applied to aspects of electrocatalysis, supercapacitors, water treatment and the like, so that the research and development of the novel hollow porous bowl-shaped carbon material are expected to relieve the sharp contradiction between the shortage of energy sources and the environmental pollution and the economic development in China. The hollow structure constructed by the hollow porous bowl-shaped carbon material effectively reduces the density of the material, so that the material has the advantages of light weight, large specific surface area and the like, and in addition, the unique porous structure obviously enhances the transmission efficiency of the material, and provides a theoretical basis for potential application values in various fields.
In order to synthesize a hollow porous carbon material with controllable morphology, structure, porosity and the like, a plurality of synthesis modes are widely researched in recent years, and most of the preparation of the hollow porous carbon material utilizes a template method and can be specifically divided into a hard template, a soft template and a self-template. Taking a hard template method as an example, a material with ideal size and morphology is selected as a template, a carbon precursor is coated on the surface of the template in the modes of electrostatic adsorption, covalent bond and the like, and then carbonization such as calcination and the like are carried out to selectively remove the template to obtain a hollow structure. Soft templates are templated by surfactant micelles or microdroplets, which, in contrast to hard template methods, omit the removal step and do not control the shape and composition of the synthesized material, since most surfactants are thermally decomposable. The template-free method is to directly carbonize some solid synthetic materials, such as metal organic frameworks and zeolitic imidazolate frameworks, into hollow porous carbon materials.
The hard template method has a greater advantage in material design than the soft template and the template-free method because the morphology, size, and pore structure of the hollow porous carbon material can be precisely controlled by adjusting a pre-designed template. However, most of the hollow structures need two-step reaction of generating a core-shell structure and dissolving a core, and the process is complicated. In addition, the selection of the target template and the defects of collapse, damage and the like which can be generated in the denucleation process limit the wide application of the template method. Therefore, a method for conveniently and effectively synthesizing a hollow porous carbon material with uniform size and morphology is urgently needed.
Disclosure of Invention
The invention aims to provide a method for preparing a hollow porous carbon nanocowl with uniform size and controllable appearance by heating in an aqueous solution.
The technical scheme for solving the technical problems is as follows: mixing the sodium oleate aqueous solution and the P123 aqueous solution, performing ultrasonic treatment for 5-15 minutes to obtain a uniform clarified solution, stirring, adding the uniform clarified solution into a 2,4-dicarbonyl benzoic acid and urotropine mixed aqueous solution, uniformly mixing, transferring the mixed solution into a high-pressure reaction kettle with a polytetrafluoroethylene lining, heating the mixed solution for 2-6 hours in an oven at the temperature of 140-180 ℃, cooling the mixed solution to room temperature, performing centrifugal separation, washing and vacuum drying to obtain the hollow porous bowl-shaped carbon material with uniform size.
In the reaction mixture, the concentration of the aqueous solution of sodium oleate is 0.2 to 0.3mol/L, and the concentration of the aqueous solution of sodium oleate is preferably 0.24mol/L.
In the reaction mixture, the concentration of the aqueous solution of P123 is 3 to 4mmol/L, and the concentration of the aqueous solution of sodium oleate is preferably 3.75mmol/L.
The molar ratio of urotropin to 2,4-dicarbonyl benzoic acid in the mixed solution is 1:1-2, and the preferred molar ratio of urotropin to 2,4-dicarbonyl benzoic acid is 1.2.
The reaction temperature of the invention is 140-180 ℃, preferably 160 ℃.
The invention is reacted for 2 to 6 hours, preferably 4 hours in a high-pressure reaction kettle with a tetrafluoroethylene lining.
The preparation method provided by the invention is simple and easy to implement, and the yield is high by taking 2,4-dicarbonylbenzoic acid as a carbon source and adopting a hydrothermal method to prepare the hollow porous bowl-shaped carbon material with uniform size and regular shape.
Drawings
FIG. 1,2 is an SEM image of the hollow porous bowl carbon material prepared in example 1.
FIG. 3 is a TEM image of the hollow porous bowl-like carbon material prepared in example 1.
FIG. 4 is BET of the hollow porous bowl carbon material prepared in example 1.
Detailed Description
The invention will be further described in detail with reference to the following figures and examples, to which, however, the scope of the invention is not limited.
Example 1
Ultrasonically mixing 1mL of sodium oleate aqueous solution containing 0.24mmol and 2mL of P123 aqueous solution containing 7.5 mu mol uniformly, adding the mixture into 30mL of aqueous solution containing 0.6mmol of 2, 4-dicarbonyl benzoic acid and 0.5mmol of urotropine under the condition of stirring, then transferring the mixture into a reaction kettle, placing the reaction kettle in an oven for reacting for 4 hours at 160 ℃ to obtain brownish red suspended substances, centrifugally separating and washing the brownish red suspended substances, and drying the brownish red suspended substances in a vacuum oven at 60 ℃ to obtain the carbon bowl. As can be seen from FIG. 1, the diameter of the prepared hollow porous bowl-shaped carbon material is about 90-140 nm, and the unique bowl-shaped structure provides a larger specific surface area, which is more favorable for loading other metal elements as a substrate material.
Example 2
Ultrasonically mixing 1mL of sodium oleate aqueous solution containing 0.24mmol and 2mL of P123 aqueous solution containing 7.5 mu mol uniformly, adding the mixture into 30mL of aqueous solution containing 0.5mmol of 2, 4-dicarbonyl benzoic acid and 0.5mmol of urotropine under the condition of stirring, transferring the mixture into a reaction kettle, placing the reaction kettle in an oven for reacting for 4 hours at 160 ℃ to obtain brownish red suspended substances, centrifugally separating and washing the brownish red suspended substances, and drying the brownish red suspended substances in a vacuum oven at 60 ℃ to obtain the hollow porous bowl-shaped carbon material.
Example 3
1mL of sodium oleate aqueous solution containing 0.24mmol of sodium oleate and 2mL of P123 aqueous solution containing 7.5 mu mol of methene are mixed uniformly by ultrasound, added into 30mL of aqueous solution containing 1mmol of 2, 4-dicarbonyl benzoic acid and 0.5mmol of urotropine under the condition of stirring, then transferred into a reaction kettle, the reaction kettle is placed into a baking oven to react for 4 hours at 160 ℃ to obtain brownish red suspended substances, and the brownish red suspended substances are centrifugally separated, washed and dried in a vacuum baking oven at 60 ℃ to obtain the hollow porous bowl-shaped carbon material.
Example 4
1mL of sodium oleate aqueous solution containing 0.24mmol and 2mL of P123 aqueous solution containing 7.5 mu mol are mixed evenly by ultrasound, added into 30mL of aqueous solution containing 0.6mmol of 2, 4-dicarbonyl benzoic acid and 0.5mmol of urotropine under the condition of stirring, then transferred into a reaction kettle, the reaction kettle is placed in a baking oven for reaction at 140 ℃ for 6 hours to obtain brownish red suspended substances, and the brownish red suspended substances are centrifugally separated, washed and dried in a vacuum baking oven at 60 ℃ to obtain the hollow porous bowl-shaped carbon material.
Example 5
1mL of sodium oleate aqueous solution containing 0.24mmol and 2mL of P123 aqueous solution containing 7.5 mu mol are mixed evenly by ultrasound, added into 30mL of aqueous solution containing 0.6mmol of 2, 4-dicarbonyl benzoic acid and 0.5mmol of urotropine under the condition of stirring, then transferred into a reaction kettle, the reaction kettle is placed in an oven for reaction at 180 ℃ for 2 hours to obtain brownish red suspended substances, and the brownish red suspended substances are centrifugally separated, washed and dried in a vacuum oven at 60 ℃ to obtain the hollow porous bowl-shaped carbon material.
Example 6
Ultrasonically mixing 1mL of sodium oleate aqueous solution containing 0.2mmol and 2mL of P123 aqueous solution containing 6 mu mol uniformly, adding the mixture into 30mL of aqueous solution containing 0.6mmol of 2, 4-dicarbonyl benzoic acid and 0.5mmol of urotropine under the condition of stirring, transferring the mixture into a reaction kettle, placing the reaction kettle in an oven for reacting for 4 hours at 160 ℃ to obtain brownish red suspended substances, centrifugally separating and washing the brownish red suspended substances, and drying the brownish red suspended substances in a vacuum oven at 60 ℃ to obtain the hollow porous bowl-shaped carbon material.
Example 7
Ultrasonically mixing 1mL of sodium oleate aqueous solution containing 0.3mmol and 2mL of P123 aqueous solution containing 8 mu mol uniformly, adding the mixture into 30mL of aqueous solution containing 0.6mmol of 2, 4-dicarbonyl benzoic acid and 0.5mmol of urotropine under the condition of stirring, transferring the mixture into a reaction kettle, placing the reaction kettle in an oven for 6 hours at 160 ℃ to obtain brownish red suspended substances, centrifugally separating and washing the brownish red suspended substances, and drying the brownish red suspended substances in a vacuum oven at 60 ℃ to obtain the hollow porous bowl-shaped carbon material.
Claims (5)
1. A preparation method of a hollow porous bowl-shaped carbon material is characterized by comprising the following steps: mixing the sodium oleate aqueous solution and the P123 aqueous solution, performing ultrasonic treatment for 5-15 minutes to obtain a uniform clarified solution, stirring, adding the uniform clarified solution into a 2,4-dicarbonyl benzoic acid and urotropine mixed aqueous solution, uniformly mixing, transferring the mixture into a high-pressure reaction kettle with a polytetrafluoroethylene lining, heating for 4 hours at the condition of an oven at 160 ℃, cooling to room temperature, performing centrifugal separation, washing and vacuum drying to obtain the hollow porous bowl-shaped carbon material with uniform size.
2. The method for producing a hollow porous bowl-shaped carbon material according to claim 1, characterized in that: the concentration of the sodium oleate water solution is 0.2-0.3 mol/L.
3. The method for producing a hollow porous bowl-shaped carbon material according to claim 1, characterized in that: the concentration of the P123 aqueous solution is 3-4 mmol/L.
4. The method for producing a hollow porous bowl-shaped carbon material according to claim 1, characterized in that: the molar ratio of the urotropine to the 2,4-dicarbonyl benzoic acid in the mixed solution is 1:1-2.
5. The method for producing a hollow porous bowl-shaped carbon material according to claim 1, characterized in that: and reacting for 2-6 hours in a high-pressure reaction kettle with tetrafluoroethylene as a lining at the temperature of 140-180 ℃.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211308195.7A CN115650204A (en) | 2022-10-25 | 2022-10-25 | Preparation method of hollow porous bowl-shaped carbon material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211308195.7A CN115650204A (en) | 2022-10-25 | 2022-10-25 | Preparation method of hollow porous bowl-shaped carbon material |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN115650204A true CN115650204A (en) | 2023-01-31 |
Family
ID=84991551
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202211308195.7A Pending CN115650204A (en) | 2022-10-25 | 2022-10-25 | Preparation method of hollow porous bowl-shaped carbon material |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN115650204A (en) |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20120237748A1 (en) * | 2011-03-16 | 2012-09-20 | Hong-Ping Lin | Porous carbon material and manufacturing method therof |
| JP2012193100A (en) * | 2011-03-16 | 2012-10-11 | Ind Technol Res Inst | Porous carbon material, and manufacturing method thereof |
| CN109553082A (en) * | 2019-01-14 | 2019-04-02 | 北京科技大学 | A kind of preparation method of hollow bowl-shape carbon material |
| CN110171812A (en) * | 2019-05-27 | 2019-08-27 | 北京科技大学 | Multi-layer porous hollow bowl-type carbon material of one kind and preparation method thereof |
| CN110255999A (en) * | 2019-06-10 | 2019-09-20 | 北京科技大学 | A kind of nitrogen oxygen codope porous hollow bowl-type carbon material and preparation method thereof |
| CN115043412A (en) * | 2022-06-08 | 2022-09-13 | 青岛科技大学 | Porous carbon material and preparation method and application thereof |
-
2022
- 2022-10-25 CN CN202211308195.7A patent/CN115650204A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20120237748A1 (en) * | 2011-03-16 | 2012-09-20 | Hong-Ping Lin | Porous carbon material and manufacturing method therof |
| JP2012193100A (en) * | 2011-03-16 | 2012-10-11 | Ind Technol Res Inst | Porous carbon material, and manufacturing method thereof |
| CN109553082A (en) * | 2019-01-14 | 2019-04-02 | 北京科技大学 | A kind of preparation method of hollow bowl-shape carbon material |
| CN110171812A (en) * | 2019-05-27 | 2019-08-27 | 北京科技大学 | Multi-layer porous hollow bowl-type carbon material of one kind and preparation method thereof |
| CN110255999A (en) * | 2019-06-10 | 2019-09-20 | 北京科技大学 | A kind of nitrogen oxygen codope porous hollow bowl-type carbon material and preparation method thereof |
| CN115043412A (en) * | 2022-06-08 | 2022-09-13 | 青岛科技大学 | Porous carbon material and preparation method and application thereof |
Non-Patent Citations (2)
| Title |
|---|
| XIN LIU等: ""Revealing the Dynamic Formation Process and Mechanism of Hollow Carbon Spheres: From Bowl to Sphere"", 《ACS SUSTAINABLE CHEMISTRY & ENGINEERING》, vol. 6, no. 2, pages 2797 - 2805 * |
| 陈春红: ""生物基水热炭材料的结构设计及其形成机理研究"", 《中国博士学位论文全文数据库工程科技Ⅰ辑(月刊)》, no. 08, pages 015 - 59 * |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN113354825B (en) | Zirconium-based metal organic framework material UiO-66(Zr) and room-temperature rapid preparation method and application thereof | |
| CN108686697A (en) | A kind of alginic acid alkali composite nitride carbon photocatalysis aerogel material and the preparation method and application thereof | |
| CN101759178B (en) | Preparation method for hollow carbon hemisphere | |
| CN112495416A (en) | MOFs-derived three-dimensional hierarchical-pore Co/NC composite material and preparation method thereof | |
| CN111250074B (en) | Method for synthesizing MOF derivative semiconductor heterojunction material by solvothermal method | |
| CN109225265B (en) | Preparation method of all-solid-state Z-type heterojunction photocatalyst | |
| CN113198505A (en) | Sodium bismuth titanate/graphite phase carbon nitride heterojunction piezoelectric photocatalyst and preparation method thereof | |
| US20220297107A1 (en) | Preparation method of embedded alkaline earth metal oxide solid alkali and application thereof in biodiesel production | |
| CN111250146A (en) | Preparation method of oxygen-enriched BiOI-BiOBr/SBA-16 composite photocatalytic material | |
| Chen et al. | Construction of a hierarchical tubular metal–organic framework composed of nanosheet arrays as a photothermal catalyst through phase transformation | |
| CN109346730B (en) | Preparation method of oxygen reduction catalyst material based on modified peanut shells | |
| CN111974436B (en) | Graphite-phase carbon nitride and preparation method thereof, and method for producing hydrogen by photocatalytic water | |
| CN115650204A (en) | Preparation method of hollow porous bowl-shaped carbon material | |
| CN113578370A (en) | Preparation method of tubular carbon nitride photocatalyst loaded by carbon material | |
| CN113289623A (en) | Copper monatomic catalyst and preparation method and application thereof | |
| CN112479223A (en) | Low-silicon nano sheet SAPO-34 molecular sieve and preparation method and application thereof | |
| CN108160090A (en) | It is a kind of using animal bone as solid alkali biodiesel catalyst of carrier and preparation method thereof | |
| CN112354559A (en) | Two-dimensional receptor molecule/hierarchical pore TiO2Composite photocatalyst, preparation method and photocatalytic application thereof | |
| CN111151301A (en) | Bifunctional heterogeneous Pd @ MIL-101@ SGO composite material and preparation method and application thereof | |
| CN111054419A (en) | For CO2Reduced semiconductor/g-C3N4Photocatalyst and preparation method thereof | |
| CN111410750B (en) | Method for repairing Co-MOF-71 metal organic framework | |
| CN111841519B (en) | Composite oxide TiO 2 -ZrO 2 Method for synthesizing aviation fuel oil precursor by catalyzing cyclopentanone | |
| CN115041234A (en) | MIL-101(Cr) @ MOF-867 core-shell material and preparation method and application thereof | |
| CN110252349B (en) | CdS @ MoS prepared by in-situ photo-deposition2Preparation method of composite photocatalyst | |
| CN114917905A (en) | Preparation and application of high-performance double-copper-structure composite nano catalytic material |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |