CN115724419A - Method for preparing hollow carbon spheres by one-pot method and application - Google Patents
Method for preparing hollow carbon spheres by one-pot method and application Download PDFInfo
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 59
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 58
- 238000000034 method Methods 0.000 title claims abstract description 31
- 238000005580 one pot reaction Methods 0.000 title claims abstract description 8
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 21
- 239000002904 solvent Substances 0.000 claims abstract description 14
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims abstract description 11
- 238000001179 sorption measurement Methods 0.000 claims abstract description 11
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 claims abstract description 7
- 238000003763 carbonization Methods 0.000 claims abstract description 6
- 239000003054 catalyst Substances 0.000 claims abstract description 6
- 239000002994 raw material Substances 0.000 claims abstract description 5
- 239000012298 atmosphere Substances 0.000 claims abstract description 4
- 238000010000 carbonizing Methods 0.000 claims abstract description 4
- 238000006243 chemical reaction Methods 0.000 claims abstract description 4
- 239000011261 inert gas Substances 0.000 claims abstract description 4
- 238000002156 mixing Methods 0.000 claims abstract description 3
- 238000006482 condensation reaction Methods 0.000 claims abstract 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 74
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical group O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 52
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 29
- AUHZEENZYGFFBQ-UHFFFAOYSA-N 1,3,5-Me3C6H3 Natural products CC1=CC(C)=CC(C)=C1 AUHZEENZYGFFBQ-UHFFFAOYSA-N 0.000 claims description 27
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 claims description 18
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical group [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 15
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 15
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 10
- 239000004094 surface-active agent Substances 0.000 claims description 10
- NBVXSUQYWXRMNV-UHFFFAOYSA-N fluoromethane Chemical compound FC NBVXSUQYWXRMNV-UHFFFAOYSA-N 0.000 claims description 8
- CWLKGDAVCFYWJK-UHFFFAOYSA-N 3-aminophenol Chemical compound NC1=CC=CC(O)=C1 CWLKGDAVCFYWJK-UHFFFAOYSA-N 0.000 claims description 7
- 229940018563 3-aminophenol Drugs 0.000 claims description 7
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 claims description 6
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 claims description 6
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 4
- 239000007864 aqueous solution Substances 0.000 claims description 4
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 claims description 2
- 229910052786 argon Inorganic materials 0.000 claims description 2
- 239000007789 gas Substances 0.000 claims description 2
- 239000001307 helium Substances 0.000 claims description 2
- 229910052734 helium Inorganic materials 0.000 claims description 2
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 2
- 239000002245 particle Substances 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 239000000243 solution Substances 0.000 claims description 2
- 238000004321 preservation Methods 0.000 claims 2
- 229920001400 block copolymer Polymers 0.000 claims 1
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- 125000001827 mesitylenyl group Chemical group [H]C1=C(C(*)=C(C([H])=C1C([H])([H])[H])C([H])([H])[H])C([H])([H])[H] 0.000 claims 1
- 239000011148 porous material Substances 0.000 abstract description 8
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- 239000003575 carbonaceous material Substances 0.000 description 5
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- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 3
- -1 Polyoxyethylene Polymers 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 230000018109 developmental process Effects 0.000 description 3
- BFMYDTVEBKDAKJ-UHFFFAOYSA-L disodium;(2',7'-dibromo-3',6'-dioxido-3-oxospiro[2-benzofuran-1,9'-xanthene]-4'-yl)mercury;hydrate Chemical compound O.[Na+].[Na+].O1C(=O)C2=CC=CC=C2C21C1=CC(Br)=C([O-])C([Hg])=C1OC1=C2C=C(Br)C([O-])=C1 BFMYDTVEBKDAKJ-UHFFFAOYSA-L 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 239000002149 hierarchical pore Substances 0.000 description 3
- DAJSVUQLFFJUSX-UHFFFAOYSA-M sodium;dodecane-1-sulfonate Chemical compound [Na+].CCCCCCCCCCCCS([O-])(=O)=O DAJSVUQLFFJUSX-UHFFFAOYSA-M 0.000 description 3
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- 239000000975 dye Substances 0.000 description 2
- MHMNJMPURVTYEJ-UHFFFAOYSA-N fluorescein-5-isothiocyanate Chemical compound O1C(=O)C2=CC(N=C=S)=CC=C2C21C1=CC=C(O)C=C1OC1=CC(O)=CC=C21 MHMNJMPURVTYEJ-UHFFFAOYSA-N 0.000 description 2
- 229920001451 polypropylene glycol Polymers 0.000 description 2
- 238000001308 synthesis method Methods 0.000 description 2
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 1
- 229920000463 Poly(ethylene glycol)-block-poly(propylene glycol)-block-poly(ethylene glycol) Polymers 0.000 description 1
- 238000003917 TEM image Methods 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 230000003321 amplification Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000000805 composite resin Substances 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000007850 fluorescent dye Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 238000003199 nucleic acid amplification method Methods 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
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Abstract
The application comprises a method for preparing hollow carbon spheres by a one-pot method and application. The method comprises the following steps: mixing a raw material containing a soft template agent with a solvent, then adding a pore-forming agent, a catalyst, phenol and aldehyde, carrying out a phenolic condensation reaction, and carbonizing in an inert gas atmosphere to obtain hollow carbon spheres; compared with the traditional preparation method, the preparation method has the advantages of simple and easy process, convenient operation, automatic removal of the template in the high-temperature carbonization process, no need of acid-base solvent, simple and economic method, environmental friendliness and contribution to large-scale production. And the hollow structure of the obtained hollow carbon sphere is connected with the ordered mesoporous pore canal, so that the mass transfer and the specific surface area are improved, and the hollow carbon sphere has the advantages of low density, good stability, uniform size, high yield and stability. Therefore, the hollow carbon spheres with the through mesoporous structure prepared by the method have great potential practical values in the aspects of adsorption, catalysis, sensing, nano medicine, energy storage, conversion, separation and the like.
Description
Technical Field
The invention belongs to the technical field of preparation of hierarchical porous carbon materials, and particularly relates to a method for preparing hollow carbon spheres by a one-pot method and application of the hollow carbon spheres.
Background
In recent years, researches and developments of porous carbon materials having different morphologies, different porosities, and different structures, particularly carbon skeleton materials having hierarchical pores, i.e., porous carbon materials in which mesopores or micropores are combined with macropores, have attracted considerable attention of researchers. When these carbon materials have a graded porosity, interconnected pores of different sizes, their potential utility value increases. The hierarchical porous carbon spheres have excellent physical and chemical properties, such as large surface area, low density, high mechanical stability, chemical inertness (acid resistance and alkaline environment), good biocompatibility, excellent carrying capacity and the like, and have great application prospects in the aspects of energy storage and conversion, adsorption and separation, catalysis, drug loading and the like.
The multi-level pore carbon spheres are developed at home and abroad, but the synthesis method is more complex. Especially, the multi-level hole hollow carbon spheres are mostly prepared by a hard template method, the template is further removed under harsh conditions of acid and alkali, the time consumption is long, the resource waste is serious, the principles of green chemistry and sustainable development are not met, meanwhile, pollution is caused, and the production amplification is not easy to realize, so that the development of a simple synthesis method and the improvement of the yield have unique significance in the field.
Disclosure of Invention
The invention belongs to a preparation method of a hollow carbon sphere with through mesopores, which adopts a soft template to synthesize in one pot, has simple method, good product dispersibility, higher yield and stable output, has a unique hollow structure and is provided with vertical mesopore channels connecting the inside and the outside.
The invention aims to form vesicles serving as templates by some ionic active agents, combine the vesicles with an amphoteric triblock copolymer, and polymerize monomers and formaldehyde under the catalysis of ammonia water. The fluorocarbon surfactant vesicle template can form a hollow structure, the amphoteric triblock copolymer can produce mesopores, and 1,3,5-trimethylbenzene can further enlarge the pores. And finally, centrifugally washing, drying to obtain the surfactant/polymerized monomer-formaldehyde resin composite material, finally carbonizing the polymer in an inert gas atmosphere, and removing the surfactant to obtain the hollow carbon spheres with the through mesopores. The method has the advantages of simple operation, low cost, high yield, uniform product, stable output and good commercialization prospect.
The object of the invention is achieved by the following measures.
According to one aspect of the present application, there is provided a one-pot method for preparing hollow carbon spheres, comprising the steps of:
mixing a raw material containing a template agent, a pore-forming agent, a catalyst, phenol and aldehyde with a solvent, reacting, and carbonizing in an inert gas atmosphere to obtain hollow carbon spheres;
the template agent is selected from one of fluorocarbon surfactant, sodium dodecyl benzene sulfonate and sodium dodecyl sulfate;
the amount of the template agent is 1-65 mg/mL solvent.
The pore-forming agent is Polyoxyethylene (PEO) polyoxypropylene (PPO) Polyoxyethylene (PEC) triblock copolymer (PEO PPO PEO);
preferably, the pore-forming agent is selected from one of F127, F108 and P123;
the mass ratio of the pore-forming agent to the template agent is 0.1-20.
The catalyst is ammonia water;
the concentration of the ammonia water is 25-28 wt%, and the dosage is 1-40 mu L/mL solvent.
The phenol is at least one of resorcinol, 3-aminophenol and hydroquinone, and the dosage is 1-50 mg/mL solvent;
the aldehyde is formaldehyde; formaldehyde is aqueous solution with the mass concentration of 37%;
the dosage ratio of the aldehyde to the phenol is formaldehyde: phenol = 1-2000 μ L, 0.01-4 g.
The solvent is an alcohol-water solution; wherein the alcohol in the alcohol aqueous solution is ethanol; the volume ratio of water to alcohol is 0.1-20.
The reaction temperature is 20-70 ℃;
the reaction time is 1-30 h.
The inactive gas is selected from nitrogen, argon and helium;
the carbonization comprises a first stage and a second stage;
in the first stage, the temperature is raised to 300-450 ℃ at a speed of 5-15 ℃/min, and the temperature is kept for 3-6 h;
in the second stage, the temperature is raised to 700-1000 ℃ at the speed of 5-10 ℃/min, and the temperature is kept for 3-6 h.
The raw material also comprises 1,3,5-trimethylbenzene;
the addition amount of the 1,3,5-trimethylbenzene is 1-60 mu L/mL solvent.
According to another aspect of the present application, there is provided a hollow carbon sphere prepared according to the method of claims 1 to 8.
The hollow carbon spheres have through mesopores;
the specific surface area of the hollow carbon sphere is 500-800 m 2 /g；
The mesoporous aperture of the hollow carbon sphere is 4-10 nm;
the particle size of the hollow carbon sphere is 400-500 nm.
According to another aspect of the present application, there is provided a use of the hollow carbon sphere in dye adsorption, wherein the hollow carbon sphere is dispersed in water to remove the dye in the water.
Compared with the prior art, the invention has the remarkable advantages that:
(1) The method adopts a soft template method, is synthesized in one pot, can automatically remove the template in the high-temperature carbonization process, and is simple, economic and environment-friendly;
(2) The hollow structure and the mesoporous pore channel are effectively combined, the hierarchical pore structure improves mass transfer and specific surface area, has low density and stable property, and greatly increases the potential application value of the hierarchical pore structure;
(3) The product has a mesoporous structure, a high specific surface, a high yield and a stable output.
Drawings
FIG. 1 is a transmission electron micrograph of a mesoporous hollow carbon sphere prepared in example 1 of the present invention, wherein the scale of FIG. 1a is 200nm and the scale of FIG. 1b is 100nm;
FIG. 2 is a scanning electron microscope image of mesoporous hollow carbon spheres prepared in example 1 of the present invention;
fig. 3 is a nitrogen adsorption data graph of mesoporous hollow carbon spheres prepared in example 1 of the present invention;
fig. 4 is a pore size distribution diagram of mesoporous hollow carbon spheres prepared in example 1 of the present invention;
fig. 5 shows the dispersion of the mesoporous hollow carbon spheres prepared in example 1 in water and the adsorption of the mesoporous hollow carbon spheres to the fluorochrome fluorescein isothiocyanate in water.
Detailed Description
The present application will be described in detail with reference to examples, but the present application is not limited to these examples.
Unless otherwise specified, the raw materials and catalysts in the examples of the present application were commercially available, wherein resorcinol was purchased from Annaiji chemical, 3-aminophenol, hydroquinone was purchased from Shanghai Hu's chemical reagent, fluorocarbon surfactant was purchased from Shanghai Ying Zhengji technology Co., ltd, sodium dodecylbenzene sulfonate was purchased from Sigma reagent, and formaldehyde, ammonia and ethanol were purchased from Shanghai pharmaceutical group chemical reagent Co., ltd.
The analysis method in the examples of the present application is as follows: performing morphology characterization on the synthesized phenolic resin polymer by using a transmission electron microscope (HT 7700, japan) and a scanning electron microscope (Hitachi-S5500, japan); the specific surface area and the pore size distribution of the material were characterized by a nitrogen desorption apparatus (ASAP 2460).
The source of the template F127 is Sigma Aldrich, the product number is P2443, the molar weight is 12600g/mol, but the source is not limited to the source, and F127 of other manufacturers is suitable for the invention as long as the same technical effect can be achieved.
Example 1
1.2g of F127 and 0.48g of fluorocarbon surfactant are weighed out and dissolved in a mixed solvent of 15mL of water and 25mL of ethanol, 0.8mL of 1,3, 5-trimethylbenzene and 1.2mL of ammonia water are added with stirring at 30 ℃, then 0.6g of resorcinol and 0.85mL of formaldehyde are added, the mixture is centrifuged out and washed several times with water and ethanol after continuous stirring for 8 hours, and the mixture is dried in an oven. And (3) heating the dried hollow mesoporous resin polymer ball to 450 ℃ at a heating rate of 10 ℃/min in a nitrogen atmosphere, preserving the temperature for 5h, then heating to 1000 ℃ at a speed of 5 ℃/min, and preserving the temperature for 4h. Finally naturally cooling toAt room temperature, as can be seen from a transmission electron microscope in fig. 1, the hollow structure of the prepared carbon sphere and the vertically through mesoporous structure are mutually through. The ordered mesopores distributed on the surface of the carbon spheres can be seen from a scanning electron microscope in FIG. 2; FIG. 3 is a graph of nitrogen adsorption data, from which it can be seen that the specific surface area is about 692m 2 (iv) g; FIG. 4 is a pore size distribution diagram, from which it can be seen that the material comprises abundant mesopores, the mesopore size being around 5.6 nm; fig. 5 shows the adsorption of the fluorochrome fluorescein isothiocyanate in water by the mesoporous hollow carbon spheres prepared under the conditions of example 1, and the adsorption amount of the fluorochrome is confirmed by an ultraviolet spectrophotometer. As can be seen from FIG. 5, the mesoporous carbon material has a rapid adsorption capacity for fluorescent dyes, and the adsorption capacity is about 51mg/g in 4h.
Example 2
1.5g of F127 and 0.75g of sodium dodecylbenzenesulfonate are weighed out and dissolved in a mixed solvent of 32mL of water and 18mL of ethanol, 1.25mL of 1,3, 5-trimethylbenzene and 0.65mL of ammonia water are added with stirring at 40 ℃, then 0.8g of resorcinol and 1.2mL of formaldehyde are added, and after continuous stirring for 10 hours, the product is centrifuged and washed several times with water and ethanol and placed in an oven for drying. And (3) heating the dried hollow mesoporous resin polymer ball to 350 ℃ at the heating rate of 5 ℃/min in the nitrogen atmosphere, preserving the heat for 3h, then heating to 800 ℃ at the heating rate of 10 ℃/min, and keeping the temperature for 6h. And finally, naturally cooling to room temperature to obtain the hollow carbon spheres penetrating through the mesopores. The characterization and test results of the obtained hollow carbon spheres were similar to those of example 1.
Example 3
0.9g of F108 and 0.54g of fluorocarbon surfactant are weighed out and dissolved in a mixed solvent of 30mL of water and 30mL of ethanol, 1.8mL of 1,3, 5-trimethylbenzene and 1.5mL of ammonia water are added under stirring at 60 ℃, then 2.7g of resorcinol and 1.8mL of formaldehyde are added, and after continuous stirring for 24 hours, the product is centrifuged and washed several times with water and ethanol and placed in an oven for drying. And (3) heating the dried hollow mesoporous resin polymer ball to 300 ℃ at a heating rate of 10 ℃/min in a nitrogen atmosphere, preserving the heat for 6h, then heating to 900 ℃ at a heating rate of 10 ℃/min, and preserving the heat for 4h. And finally, naturally cooling to room temperature to obtain the hollow carbon spheres penetrating through the mesopores. The characterization and test results of the obtained hollow carbon spheres were similar to those of example 1.
Example 4
0.875g of P123 and 0.42g of sodium dodecylsulfonate were weighed out and dissolved in a mixed solvent of 20mL of water and 15mL of ethanol, 1.4mL of 1,3, 5-trimethylbenzene and 0.98mL of ammonia water were added with stirring at 30 ℃, then 0.63g of 3-aminophenol and 0.75mL of formaldehyde were added, and after continuous stirring for 12 hours, the product was centrifuged and washed several times with water and ethanol and placed in an oven for drying. And (3) heating the dried hollow mesoporous resin polymer ball to 400 ℃ at a heating rate of 15 ℃/min in a nitrogen atmosphere, preserving the heat for 3h, then heating to 900 ℃ at a speed of 5 ℃/min, and keeping the temperature for 6h. And finally, naturally cooling to room temperature to obtain the hollow carbon spheres penetrating through the mesopores. The characterization and test results of the obtained hollow carbon spheres are similar to those of example 1.
Example 5
1.2g of F127 and 0.42g of sodium dodecylsulfonate are weighed out and dissolved in a mixed solvent of 18mL of water and 16mL of ethanol, 0.85mL of 1,3, 5-trimethylbenzene and 0.96mL of ammonia water are added with stirring at 70 ℃, then 0.8g of 3-aminophenol and 1.2mL of formaldehyde are added, and after continuous stirring for 6 hours, the product is centrifuged and washed several times with water and ethanol and placed in an oven for drying. And (3) raising the temperature of the dried hollow mesoporous resin polymer ball to 400 ℃ at a heating rate of 10 ℃/min in a nitrogen atmosphere, preserving the heat for 3h, then raising the temperature to 800 ℃ at a rate of 10 ℃/min, and preserving the heat for 6h. And finally, naturally cooling to room temperature to obtain the hollow carbon spheres penetrating through the mesopores. The characterization and test results of the obtained hollow carbon spheres were similar to those of example 1.
Example 6
0.77g of P123 and 1.2g of sodium dodecylbenzenesulfonate are weighed out and dissolved in a mixed solvent of 45mL of water and 32mL of ethanol, 2.7mL of 1,3, 5-trimethylbenzene and 1.8mL of ammonia water are added with stirring at 45 ℃, then 1.3g of resorcinol and 1.5mL of formaldehyde are added, the mixture is stirred for 12 hours, centrifuged and washed several times with water and ethanol, and the mixture is dried in an oven. And (3) heating the dried hollow mesoporous resin polymer ball to 350 ℃ at a heating rate of 5 ℃/min in a nitrogen atmosphere, preserving the heat for 3h, then heating to 700 ℃ at a speed of 10 ℃/min, and preserving the heat for 15h. And finally, naturally cooling to room temperature to obtain the hollow carbon spheres penetrating through the mesopores. The characterization and test results of the obtained hollow carbon spheres were similar to those of example 1.
Example 7
3.2g of F108 and 1.6g of fluorocarbon surfactant are weighed out and dissolved in a mixed solvent of 35mL of water and 45mL of ethanol, 1.6mL of 1,3, 5-trimethylbenzene and 0.8mL of ammonia water are added with stirring at 30 ℃, then 2.4g of 3-aminophenol and 1.6mL of formaldehyde are added, the mixture is stirred continuously for 24 hours, and the product is centrifuged and washed several times with water and ethanol and placed in an oven for drying. And (3) heating the dried hollow mesoporous resin polymer spheres with the surface to 400 ℃ at the heating rate of 5 ℃/min in the nitrogen atmosphere, preserving the heat for 3h, then heating to 900 ℃ at the heating rate of 5 ℃/min, and keeping the temperature for 6h. And finally, naturally cooling to room temperature to obtain the hollow carbon spheres penetrating through the mesopores. The characterization and test results of the obtained hollow carbon spheres were similar to those of example 1.
Example 8
1.15g of P123 and 1.38g of fluorocarbon surfactant were weighed out and dissolved in a mixed solvent of 8mL of water and 15mL of ethanol, 1.2mL of 1,3, 5-trimethylbenzene and 0.8mL of aqueous ammonia were added with stirring at 55 ℃, then 0.56g of resorcinol and 1.2mL of formaldehyde were added, and after continuous stirring for 24 hours, the product was centrifuged and washed several times with water and ethanol and placed in an oven for drying. And (3) raising the temperature of the dried hollow mesoporous resin polymer ball to 300 ℃ at a heating rate of 10 ℃/min in a nitrogen atmosphere, preserving the heat for 6h, then raising the temperature to 1000 ℃ at a rate of 10 ℃/min, and preserving the heat for 4h. And finally, naturally cooling to room temperature to obtain the hollow carbon spheres with through mesopores. The characterization and test results of the obtained hollow carbon spheres were similar to those of example 1.
Example 9
0.4g of F127 and 1.2g of sodium dodecylbenzenesulfonate were weighed out and dissolved in a mixed solvent of 10mL of water and 30mL of ethanol, 0.8mL of 1,3, 5-trimethylbenzene and 1.2mL of aqueous ammonia were added under stirring at 40 ℃, then 0.4g of resorcinol and 0.75mL of formaldehyde were added, and after continuous stirring for 10 hours, the product was centrifuged and washed several times with water and ethanol and placed in an oven for drying. And (3) raising the temperature of the dried hollow mesoporous resin polymer ball to 350 ℃ at a heating rate of 10 ℃/min in a nitrogen atmosphere, preserving the heat for 5h, then raising the temperature to 800 ℃ at a rate of 5 ℃/min, and preserving the heat for 3h. And finally, naturally cooling to room temperature to obtain the hollow carbon spheres penetrating through the mesopores. The characterization and test results of the obtained hollow carbon spheres were similar to those of example 1.
Example 10
1.5g of F127 and 0.1g of sodium dodecylsulfonate were weighed out and dissolved in a mixed solvent of 30mL of water and 18mL of ethanol, 1.6mL of 1,3, 5-trimethylbenzene and 0.8mL of ammonia water were added with stirring at 70 ℃, then 0.6g of 3-aminophenol and 0.75mL of formaldehyde were added, and after continuous stirring for 30 hours, the product was centrifuged and washed several times with water and ethanol and placed in an oven for drying. And (3) heating the dried hollow mesoporous resin polymer ball to 400 ℃ at a heating rate of 10 ℃/min in a nitrogen atmosphere, preserving the heat for 3h, then heating to 800 ℃ at a heating rate of 10 ℃/min, and keeping the temperature for 6h. And finally, naturally cooling to room temperature to obtain the hollow carbon spheres penetrating through the mesopores. The characterization and test results of the obtained hollow carbon spheres were similar to those of example 1.
Although the present application has been described with reference to a few embodiments, it should be understood that various changes, substitutions and alterations can be made herein without departing from the spirit and scope of the application as defined by the appended claims.
Claims (10)
1. A method for preparing hollow carbon spheres by a one-pot method is characterized by comprising the following steps:
mixing a raw material containing a soft template agent and a pore-forming agent with a solvent, then adding a catalyst, phenol and aldehyde to perform a phenolic condensation reaction, and carbonizing in an inert gas atmosphere to obtain hollow carbon spheres;
the soft template agent is selected from one of fluorocarbon surfactant, sodium dodecyl benzene sulfonate and sodium dodecyl sulfate.
2. The method of claim 1,
the amount of the soft template agent is 1-65 mg/mL solvent;
the pore-forming agent is an amphoteric block copolymer;
preferably, the pore-forming agent is selected from one of F127, F108 and P123;
the mass ratio of the pore-forming agent to the soft template agent is 0.1-20.
3. The method of claim 1,
the catalyst is ammonia water;
the concentration of the ammonia water is 25-28 wt%, and the dosage is 1-40 mu L/mL solvent.
4. The method of claim 1,
the phenol is at least one of resorcinol, 3-aminophenol and hydroquinone, and the dosage is 1-50 mg/mL solvent;
the aldehyde is formaldehyde; formaldehyde is aqueous solution with the mass concentration of 37%;
the dosage ratio of the aldehyde to the phenol is formaldehyde: phenol = 1-2000 μ L, 0.01-4 g.
5. The method of claim 1,
the solvent is an alcohol-water solution;
the alcohol in the alcohol aqueous solution is ethanol; the volume ratio of water to alcohol is 0.1-20.
6. The method of claim 1,
the reaction temperature is 20-70 ℃;
the reaction time is 1-30 h.
7. The method of claim 1,
the inactive gas is selected from nitrogen, argon and helium;
the carbonization comprises a first stage and a second stage;
the temperature rise rate of the first stage is 5-15 ℃/min; the carbonization temperature is 300-450 ℃; the heat preservation time is 3-6 h;
the temperature rise rate of the second stage is 5-10 ℃/min; the carbonization temperature is 700-1000 ℃; the heat preservation time is 3-6 h.
8. The method of claim 1, wherein the feedstock further comprises a pore-expanding agent;
the addition amount of the pore-expanding agent is 1-60 mu L/mL of solvent;
preferably, the pore-expanding agent is 1,3,5-trimethylbenzene.
9. A hollow carbon sphere produced by the method according to claims 1 to 8,
the spherical shell of the hollow carbon sphere is provided with a hole; preferably, the holes are mesopores which penetrate through the spherical shell along the radial direction;
the specific surface area of the hollow carbon sphere is 500-800 m 2 /g；
The mesoporous aperture of the hollow carbon sphere is 4-10 nm;
the particle size of the hollow carbon sphere is 400-500 nm.
10. Use of a hollow carbon sphere according to claim 9 for dye adsorption;
preferably for adsorbing the dye in the liquid phase.
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| CN112758910A (en) * | 2019-11-04 | 2021-05-07 | 中国科学院大连化学物理研究所 | Mesoporous nano carbon sphere and preparation method and application thereof |
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