CN117534058B - High-specific-surface raspberry-shaped mesoporous carbon ball and preparation method thereof - Google Patents
High-specific-surface raspberry-shaped mesoporous carbon ball and preparation method thereof Download PDFInfo
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- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 title claims abstract description 54
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 239000000693 micelle Substances 0.000 claims abstract description 66
- 229910004298 SiO 2 Inorganic materials 0.000 claims abstract description 40
- 238000001035 drying Methods 0.000 claims abstract description 28
- 238000006243 chemical reaction Methods 0.000 claims abstract description 27
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims abstract description 24
- 229920001690 polydopamine Polymers 0.000 claims abstract description 20
- 239000011246 composite particle Substances 0.000 claims abstract description 19
- OWMVSZAMULFTJU-UHFFFAOYSA-N bis-tris Chemical compound OCCN(CCO)C(CO)(CO)CO OWMVSZAMULFTJU-UHFFFAOYSA-N 0.000 claims abstract description 11
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 73
- 239000000243 solution Substances 0.000 claims description 67
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 47
- VYFYYTLLBUKUHU-UHFFFAOYSA-N dopamine Chemical compound NCCC1=CC=C(O)C(O)=C1 VYFYYTLLBUKUHU-UHFFFAOYSA-N 0.000 claims description 38
- 229960000583 acetic acid Drugs 0.000 claims description 27
- 238000005406 washing Methods 0.000 claims description 23
- 229960003638 dopamine Drugs 0.000 claims description 19
- 238000003756 stirring Methods 0.000 claims description 19
- 238000000034 method Methods 0.000 claims description 18
- 239000012456 homogeneous solution Substances 0.000 claims description 17
- 239000002077 nanosphere Substances 0.000 claims description 16
- 239000003921 oil Substances 0.000 claims description 15
- 239000007864 aqueous solution Substances 0.000 claims description 13
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 10
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 10
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 10
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 10
- 230000001476 alcoholic effect Effects 0.000 claims description 8
- 238000010000 carbonizing Methods 0.000 claims description 8
- 238000005253 cladding Methods 0.000 claims description 8
- 239000008367 deionised water Substances 0.000 claims description 8
- 229910021641 deionized water Inorganic materials 0.000 claims description 8
- 239000012362 glacial acetic acid Substances 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 7
- 239000007853 buffer solution Substances 0.000 claims description 6
- 239000002245 particle Substances 0.000 claims description 6
- 238000010306 acid treatment Methods 0.000 claims description 5
- 229920000075 poly(4-vinylpyridine) Polymers 0.000 claims description 5
- 230000035484 reaction time Effects 0.000 claims description 5
- 239000000377 silicon dioxide Substances 0.000 claims description 5
- 235000012239 silicon dioxide Nutrition 0.000 claims description 5
- 238000009210 therapy by ultrasound Methods 0.000 claims description 3
- 239000000463 material Substances 0.000 abstract description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 abstract description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 6
- 229910052799 carbon Inorganic materials 0.000 abstract description 6
- 239000000872 buffer Substances 0.000 abstract description 5
- 229910052757 nitrogen Inorganic materials 0.000 abstract description 3
- 238000005530 etching Methods 0.000 abstract description 2
- 239000000758 substrate Substances 0.000 abstract 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 29
- 239000004793 Polystyrene Substances 0.000 description 21
- 238000001000 micrograph Methods 0.000 description 5
- 238000003763 carbonization Methods 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 230000005540 biological transmission Effects 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000003795 desorption Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- CTENFNNZBMHDDG-UHFFFAOYSA-N Dopamine hydrochloride Chemical compound Cl.NCCC1=CC=C(O)C(O)=C1 CTENFNNZBMHDDG-UHFFFAOYSA-N 0.000 description 1
- 239000007983 Tris buffer Substances 0.000 description 1
- 238000005411 Van der Waals force Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 239000000908 ammonium hydroxide Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 229960001149 dopamine hydrochloride Drugs 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 238000003760 magnetic stirring Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 238000001338 self-assembly Methods 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 229920000428 triblock copolymer Polymers 0.000 description 1
- LENZDBCJOHFCAS-UHFFFAOYSA-N tris Chemical compound OCC(N)(CO)CO LENZDBCJOHFCAS-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- 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
- C01B32/15—Nano-sized carbon materials
-
- 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
- C01B32/15—Nano-sized carbon materials
- C01B32/18—Nanoonions; Nanoscrolls; Nanohorns; Nanocones; Nanowalls
Abstract
The invention relates to a raspberry-shaped mesoporous carbon ball with a high specific surface and a preparation method thereof, comprising the following steps: PS-PVP-PEO single micelle is taken as an assembly primitive, and SiO 2 The spheres are taken as substrates, and SiO is obtained through oil bath reaction 2 A @ single micelle superstructure; in SiO form 2 The super structure of @ single micelle is used as a template, polydopamine is used as a carbon source, bis (2-hydroxyethyl) amino tris (hydroxymethyl) methane is used as a buffer, after secondary oil bath reaction, the SiO wrapped by polydopamine is obtained by centrifugal drying 2 Composite particles of @ single micelles; roasting the composite particles under the protection of nitrogen, and etching by using hydrofluoric acid to obtain the raspberry-shaped mesoporous carbon spheres. The raspberry-shaped mesoporous carbon sphere is of a hollow structure, the shell layer of the carbon sphere is of a spherical mesoporous super structure which is regularly arranged, and each carbon sphere is provided with obvious open broken holes. The open broken holes and the abundant and special mesoporous super structure which exist stably greatly improve the specific surface area of the material, increase the active sites of chemical reaction and expand the application space of the mesoporous carbon sphere.
Description
Technical Field
The invention belongs to the technical field of mesoporous superstructure, and particularly relates to a raspberry-shaped mesoporous carbon ball with a high specific surface and a preparation method thereof.
Background
The simple construction elements are assembled into a complex super structure according to a certain rule, often show completely different properties from the assembled units, and particularly for three-dimensional mesoporous super structure materials with unique structures, rich mesopores, controllable configuration and high surface area, the three-dimensional mesoporous super structure materials are widely applied to the fields of energy storage, catalysis, environment, adsorption, biomedicine and the like due to rich active sites and rapid electron transfer dynamics.
In the traditional mesoporous super structure synthesis strategy of the template-free method or the hard template method, the building units are often uncontrollable, and the uncontrollability leads to extremely non-uniform quantity, size, aperture and thickness of the mesoporous super structure units, and even causes irregular aggregation and serious deformation of the nanoparticle building units; although mesoporous superstructures can be precisely synthesized by the soft template method using amphiphilic surfactant micelles as templates, the super particles obtained by the method generally have multilayer mesopores, resulting in the generation of ultra-long material transport channels and extremely low mass transfer kinetics.
Disclosure of Invention
The invention aims to provide raspberry-like mesoporous carbon spheres with high specific surface.
The first object of the invention is implemented by the following technical scheme: the raspberry-shaped mesoporous carbon sphere with the high specific surface is of a hollow structure, a shell layer is provided with a mesoporous super structure and an open broken hole, the particle size of the mesoporous carbon sphere is 300-400nm, and the number of the super structure protrusions on the mesoporous carbon sphere is 70-360.
The second object of the present invention is to provide a method for preparing the raspberry-shaped mesoporous carbon sphere with a high specific surface, which adopts a soft and hard dual-template method to prepare the raspberry-shaped mesoporous carbon sphere, wherein the mesoporous carbon sphere is of a hollow structure, and a shell layer is provided with a mesoporous super structure and an open broken hole, so that the specific surface area of the mesoporous carbon sphere can be greatly improved, and the application space of the mesoporous carbon sphere can be greatly effectively expanded.
The second object of the invention is implemented by the following technical scheme: a preparation method of raspberry-shaped mesoporous carbon spheres with high specific surface area comprises the following steps:
(1) SiO is made of 2 Uniformly dispersing the spherical hard template in ethanol solution, dropwise adding PS-PVP-PEO single micelle soft template acetic acid solution under intense stirring, adding ammonia water to regulate pH value of the reaction solution, reacting, purifying, and drying to obtain SiO 2 A @ PS-PVP-PEO single micelle super structure;
(2) To SiO 2 Adding bis (2-hydroxyethyl) amino tris (hydroxymethyl) methane buffer solution into the super-structural alcohol solution of the PS-PVP-PEO single micelle, performing ultrasonic treatment to uniformly disperse the buffer solution, adding polydopamine, and performing oil bath reaction to obtain polydopamine-coated SiO 2 Composite particles of @ single micelles;
(3) Centrifuging, washing and drying to obtain a pure sample, and roasting in a nitrogen atmosphere to obtain SiO 2 A @ mesoporous carbon superstructure; and (3) treating with hydrofluoric acid aqueous solution, and removing the silicon dioxide template to obtain the raspberry-shaped mesoporous carbon spheres with high specific surface area.
Preferably, the PS-PVP-PEO single micelle in the step (1) is PEO 113 -PVP 60 -PS 28 、PEO 113 -PVP 68 -PS 60 、PEO 113 -PVP 44 -PS 97 And PEO 113 -PVP 98 -PS 142 One of them.
Preferably, the concentration of the PS-PVP-PEO single micelle acetic acid solution is 1-3 mg/mL; siO (SiO) 2 The concentration of the super-structured alcohol solution of the @ PS-PVP-PEO single micelle is 3-7 mg/mL.
Preferably, the reaction in the step (1) is a magnetic stirring reaction, the stirring speed is 300-600 r/min, the time is 0.5-2 h, the oil bath reaction time in the step (2) is 5-7 h, and the reactions are all carried out at normal temperature.
Preferably, the centrifugal rotating speed in the step (3) is 8000-15000 r/min, the washing condition is 95% ethanol solution, and the washing times are 2-6 times.
Preferably, the drying temperature in the step (3) is 50-80 ℃ and the drying time is 20-30 h.
Preferably, the roasting in the step (3) is performed under a nitrogen atmosphere, and the roasting is performed in two stages, wherein the roasting temperature in the first stage is 300-400 ℃, the roasting time is 1-3h, the roasting temperature in the second stage is 600-900 ℃, and the roasting time is 2-4 h.
Preferably, the hydrofluoric acid in the step (3) is 3-8% (V/V), and the acid treatment time is 20-30 h.
The invention has the advantages that:
1. the invention takes triblock polymer PS-PVP-PEO single micelle as a soft template, siO 2 The nanospheres are hard templates, the mesoporous super-structure soft and hard double templates are formed by self-assembly under the action of hydrogen bonds and Van der Waals force after simple stirring, dopamine is further used as a carbon source, the carbon source is wrapped on the mesoporous super-structure templates through oil bath reaction at normal temperature, and finally the templates are removed through high-temperature and acid etching, so that the raspberry-shaped mesoporous carbon spheres are obtained. The soft and hard double-template method can ensure the controllability of the super-structure building unit and maintain the rapid mass transfer dynamics of the material.
2. The raspberry-like mesoporous carbon sphere has the particle size of 300-400nm and the specific surface area of up to 685-685 m 2 And/g, useful and abundant mesoporous super-structural units, and solves the difficult problem of synthesizing an open hollow mesoporous carbon super-structure.
3. The invention does not need high temperature and high pressure during the synthesis of the mesoporous superstructure template and the coating of the dopamine, and can realize the regulation and control of the size, the number and the thickness of the superstructure on the mesoporous carbon sphere by adjusting the model, the pH value or the addition amount of the dopamine of the PS-PVP-PEO single micelle, and the process is simple.
Drawings
In order to more clearly illustrate the embodiments of the invention or the technical solutions in the prior art, the drawings that are required in the embodiments or the description of the prior art will be briefly described, it being obvious that the drawings in the following description are only some embodiments of the invention, and that other drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
FIG. 1 is a scanning electron microscope image of the raspberry-like mesoporous carbon sphere prepared in example 1 of the present invention;
FIG. 2 is a transmission electron microscope image of the raspberry-like mesoporous carbon spheres prepared in example 1 of the present invention;
FIG. 3 is a scanning electron microscope image of the raspberry-like mesoporous carbon sphere prepared in example 2 of the present invention.
FIG. 4 is a scanning electron microscope image of the raspberry-like mesoporous carbon sphere prepared in example 3 of the present invention.
FIG. 5 is a scanning electron microscope image of the raspberry-like mesoporous carbon sphere prepared in example 4 of the present invention.
FIG. 6 is a drawing showing nitrogen adsorption and desorption of samples obtained in examples 1 to 4 of the present invention.
Detailed Description
The following description of the embodiments of the present invention will be made clearly and completely with reference to the accompanying drawings, in which it is apparent that the embodiments described are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
The experiment includes the following raw materials: a triblock copolymer of acetic acid (AR, 99.5%), tetraethyl silicate (TEOS, AR, 37.0-40.0%), absolute ethanol (AR, > 99.7%) and ammonium hydroxide (AR, 25-28%), poly (ethylene oxide) -block-poly (4-vinylpyridine) -block-polystyrene (PEO-PVP-PS), dopamine hydrochloride (AR), hydrofluoric acid (HF, AR, > 40.0%) and bis (2-hydroxyethyl) aminotri (hydroxymethyl) methane (tris-buffer, > 99.9%).
The invention is further described below by way of examples.
Example 1
Preparation method of mesoporous carbon spheres
S1, preparing a super-structure soft and hard double template: siO to be prepared by St method 2 The nanospheres were dispersed with ethanol to form a 1.0 mg/mL homogeneous alcoholic solution. 20 mg PEO 113 -PVP 44 -PS 97 The single micelle was dispersed in 10 mL glacial acetic acid to form a single micelle acetic acid solution. Dropwise addition of 2 mL single micelle acetic acid solution to SiO 2 Nanometer scaleIn a spherical homogeneous solution. Adding 25 mu L ammonia water for 5 min, magnetically stirring for 1h at 500 r/min, centrifuging, washing, and drying to obtain SiO 2 @PEO 113 -PVP 44 -PS 97 A single micelle super structure template.
S2, dopamine cladding template: 1mg of SiO 2 @PEO 113 -PVP 44 -PS 97 The single micelle superstructures were dispersed into 0.5 mL ethanol solution, followed by the addition of 1.5 mL deionized water to form a uniformly dispersed solution. Then 2 mg bis (2-hydroxyethyl) aminotri (hydroxymethyl) methane buffer was added to the solution and stirring was continued until a homogeneous solution was formed. The homogeneous solution was transferred to a round bottom flask and 5 mg polydopamine was added. Then placing the mixture into an oil bath reaction device for reaction at 25 ℃ for 6 h, centrifuging and drying to obtain polydopamine coated SiO 2 @PEO 113 -PVP 44 -PS 97 Composite particles of single micelles.
S3, carbonizing dopamine and removing a template: the composite particles were heat treated at 350 ℃ under nitrogen atmosphere for 2 h to remove the single micelle soft templates. Then, the temperature was further raised to 800 ℃ and calcined 3h, and deep carbonization was performed. After cooling to room temperature, 24 h was treated with 5% (V/V) HF aqueous solution to remove SiO 2 And (5) hard template to obtain the mesoporous carbon spheres.
Example 2
The preparation method of the mesoporous carbon sphere comprises the following steps:
s1, preparing a super-structure soft and hard double template: siO to be prepared by St method 2 The nanospheres were dispersed with ethanol to form a 1.0 mg/mL homogeneous alcoholic solution. 20 mg PEO 113 -PVP 98 -PS 142 The single micelle was dispersed in 10 mL glacial acetic acid to form a single micelle acetic acid solution. Dropwise addition of 2 mL single micelle acetic acid solution to SiO 2 The nanospheres are in homogeneous phase solution. Adding 25 mu L ammonia water for 5 min, magnetically stirring for 1h at 500 r/min, centrifuging, washing, and drying to obtain SiO 2 @ PEO 113 -PVP 98 -PS 142 A single micelle super structure template.
S2, dopamine cladding template: 1mg of SiO 2 @PEO 113 -PVP 98 -PS 142 The single micelle superstructures were dispersed into 0.5 mL ethanol solution, followed by the addition of 1.5 mL deionized water to form a uniformly dispersed solution. Then 2 mg bis (2-hydroxyethyl) aminotri (hydroxymethyl) methane buffer was added to the solution and stirring was continued until a homogeneous solution was formed. The homogeneous solution was transferred to a round bottom flask and 5 mg polydopamine was added. Then placing the mixture into an oil bath reaction device for reaction at 25 ℃ for 6 h, centrifuging and drying to obtain polydopamine coated SiO 2 @ PEO 113 -PVP 98 -PS 142 Composite particles of single micelles.
S3, carbonizing dopamine and removing a template: the composite particles were heat treated at 350 ℃ under nitrogen atmosphere for 2 h to remove the single micelle soft templates. Then, the temperature was further raised to 800 ℃ and calcined 3h, and deep carbonization was performed. After cooling to room temperature, 24 h was treated with 5% (V/V) HF aqueous solution to remove SiO 2 And (5) hard template to obtain the mesoporous carbon spheres.
Example 3
The preparation method of the mesoporous carbon sphere comprises the following steps:
s1, preparing a super-structure soft and hard double template: siO to be prepared by St method 2 The nanospheres were dispersed with ethanol to form a 1.0 mg/mL homogeneous alcoholic solution. 20 mg PEO 113 -PVP 44 -PS 97 The single micelle was dispersed in 10 mL glacial acetic acid to form a single micelle acetic acid solution. Dropwise addition of 2 mL single micelle acetic acid solution to SiO 2 The nanospheres are in homogeneous phase solution. Adding 11 mu L ammonia water for 5 min, magnetically stirring for 1h at 500 r/min, centrifuging, washing, and drying to obtain SiO 2 @PEO 113 -PVP 44 -PS 97 A single micelle super structure template.
S2, dopamine cladding template: 1mg of SiO 2 @PEO 113 -PVP 44 -PS 97 The single micelle superstructures were dispersed into 0.5 mL ethanol solution, followed by the addition of 1.5 mL deionized water to form a uniformly dispersed solution. Then 2 mg bis (2-hydroxyethyl) aminotri (hydroxymethyl) methane buffer was added to the solution and stirring was continued until a homogeneous solution was formed. The homogeneous solution was transferred to a round bottom flask and 5 mg polydopamine was added. Then put into an oil bath reaction deviceAfter the reaction is carried out at 25 ℃ for 6 h, the SiO wrapped by polydopamine is obtained after centrifugation and drying 2 @ PEO 113 -PVP 44 -PS 97 Composite particles of single micelles.
S3, carbonizing dopamine and removing a template: the composite particles were heat treated at 350 ℃ under nitrogen atmosphere for 2 h to remove the single micelle soft templates. Then, the temperature was further raised to 800 ℃ and calcined 3h, and deep carbonization was performed. After cooling to room temperature, 24 h was treated with 5% (V/V) HF aqueous solution to remove SiO 2 And (5) hard template to obtain the mesoporous carbon spheres.
Example 4
The preparation method of the mesoporous carbon sphere comprises the following steps:
s1, preparing a super-structure soft and hard double template: siO to be prepared by St method 2 The nanospheres were dispersed with ethanol to form a 1.0 mg/mL homogeneous alcoholic solution. 20 mg PEO 113 -PVP 44 -PS 97 The single micelle was dispersed in 10 mL glacial acetic acid to form a single micelle acetic acid solution. Dropwise addition of 2 mL single micelle acetic acid solution to SiO 2 The nanospheres are in homogeneous phase solution. Adding 25 mu L ammonia water for 5 min, magnetically stirring for 1h at 500 r/min, centrifuging, washing, and drying to obtain SiO 2 @PEO 113 -PVP 44 -PS 97 A single micelle super structure template.
S2, dopamine cladding template: 1mg of SiO 2 @PEO 113 -PVP 44 -PS 97 The single micelle superstructures were dispersed into 0.5 mL ethanol solution, followed by the addition of 1.5 mL deionized water to form a uniformly dispersed solution. Then 2 mg bis (2-hydroxyethyl) aminotri (hydroxymethyl) methane buffer was added to the solution and stirring was continued until a homogeneous solution was formed. The homogeneous solution was transferred to a round bottom flask and 15 mg polydopamine was added. Then placing the mixture into an oil bath reaction device for reaction at 25 ℃ for 6 h, centrifuging and drying to obtain polydopamine coated SiO 2 @PEO 113 -PVP 44 -PS 97 Composite particles of single micelles.
S3, carbonizing dopamine and removing a template: the composite particles were heat treated at 350 ℃ under nitrogen atmosphere for 2 h to remove the single micelle soft templates. Then, warmThe temperature is further raised to 800 ℃ to calcine 3h, and deep carbonization is carried out. After cooling to room temperature, 24 h was treated with 5% (V/V) HF aqueous solution to remove SiO 2 And (5) hard template to obtain the mesoporous carbon spheres.
The mesoporous carbon spheres obtained in examples 1-4 were subjected to scanning electron microscope analysis and transmission electron microscope analysis, wherein the scanning electron microscope and transmission electron microscope are shown in fig. 1-5, and the nitrogen adsorption and desorption drawing of the samples obtained in examples 1-4 is shown in fig. 6.
As can be seen from fig. 1 and 2, the mesoporous carbon sphere prepared in example 1 shows a raspberry-like morphology, has a hollow structure as a whole, has closely and regularly arranged superstructure protrusions on the surface, and has obvious broken holes on each carbon sphere. The particle size diameter is about 300-400nm, the super-structure unit diameter is about 20-30 nm, the size, shape and size of the broken hole are different, and the specific surface area of the material is up to 740 m 2 /g。
As can be seen from FIG. 3, the mesoporous carbon spheres prepared in example 2 have significantly larger super-structural units, the diameters of the super-structural units are about 60-80 and nm, and the specific surface area of the material is 535 and 535 m 2 /g。
As can be seen from FIG. 4, the mesoporous carbon sphere prepared in example 3 has significantly fewer super-structural units, the super-structural units cannot be closely arranged, a large-scale flat area appears, and the specific surface area of the material is 255 m 2 /g。
As can be seen from FIG. 5, the mesoporous carbon sphere prepared in example 4 has a relatively high shell thickness, the superstructure is not revealed basically, and the specific surface area of the material is only 65 m 2 /g。
The foregoing description of the preferred embodiments of the invention is not intended to be limiting, but rather is intended to cover all modifications, equivalents, alternatives, and improvements that fall within the spirit and scope of the invention.
Claims (4)
1. The raspberry-shaped mesoporous carbon sphere with the high specific surface is characterized in that the mesoporous carbon sphere is of a hollow structure, a shell layer is provided with a mesoporous super structure and an open broken hole, the particle size of the mesoporous carbon sphere is 300-400nm, and the number of the super structure protrusions on the mesoporous carbon sphere is 70-360; the preparation method comprises the following steps:
s1, preparing a super-structure soft and hard double template: siO to be prepared by St method 2 Dispersing the nanospheres with ethanol to form a 1.0 mg/mL homogeneous alcoholic solution; 20 mg PEO 113 -PVP 44 -PS 97 The single micelle is dispersed in 10 mL glacial acetic acid to form single micelle acetic acid solution; dropwise addition of 2 mL single micelle acetic acid solution to SiO 2 The nanospheres are in homogeneous phase solution; adding 11 or 25 μL ammonia water in 5 min, magnetically stirring for reaction at 300-600 r/min for 0.5-2 h, centrifuging, washing, and drying to obtain SiO 2 @PEO 113 -PVP 44 -PS 97 A single micelle super structure template; wherein PVP is poly (4-vinylpyridine);
s2, dopamine cladding template: 1mg of SiO 2 @PEO 113 -PVP 44 -PS 97 Dispersing the single micelle super structure into 0.5 mL ethanol solution, and then adding 1.5 mL deionized water to form a uniformly dispersed solution; then adding 2 mg bis (2-hydroxyethyl) aminotri (hydroxymethyl) methane buffer solution into the solution, and continuously stirring until a homogeneous solution is formed; the homogeneous solution was transferred to a round bottom flask and 5 mg polydopamine was added; then placing the mixture in an oil bath reaction device, wherein the oil bath reaction time is 5-7 h, and the reactions are all carried out at normal temperature; centrifuging, washing and drying to obtain SiO coated with polydopamine 2 @PEO 113 -PVP 44 -PS 97 The composite particles of the single micelle have centrifugal rotation speed of 8000-15000 r/min, washing condition of 95% ethanol solution, washing times of 2-6 times, drying temperature of 50-80 ℃ and drying time of 20-30 h;
s3, carbonizing dopamine and removing a template: roasting the composite particles in nitrogen atmosphere to obtain SiO 2 A @ mesoporous carbon superstructure; treating with hydrofluoric acid aqueous solution, and removing the silicon dioxide template to obtain raspberry-shaped mesoporous carbon spheres with high specific surface; roasting is divided into two stages, wherein the roasting temperature in the first stage is 300-400 ℃, the roasting time is 1-3h, the roasting temperature in the second stage is 600-900 ℃, and the roasting time is 2-4 h; the volume percentage of the hydrofluoric acid aqueous solution is 3-8%, and the acid treatment time is 20-30 h.
2. The method for preparing the raspberry-like mesoporous carbon sphere with high specific surface area according to claim 1, which is characterized by comprising the following steps:
s1, preparing a super-structure soft and hard double template: siO to be prepared by St method 2 Dispersing the nanospheres with ethanol to form a 1.0 mg/mL homogeneous alcoholic solution; 20 mg PEO 113 -PVP 44 -PS 97 The single micelle is dispersed in 10 mL glacial acetic acid to form single micelle acetic acid solution; dropwise addition of 2 mL single micelle acetic acid solution to SiO 2 The nanospheres are in homogeneous phase solution; adding 11 or 25 μL ammonia water in 5 min, magnetically stirring for reaction at 300-600 r/min for 0.5-2 h, centrifuging, washing, and drying to obtain SiO 2 @PEO 113 -PVP 44 -PS 97 A single micelle super structure template; wherein PVP is poly (4-vinylpyridine);
s2, dopamine cladding template: 1mg of SiO 2 @PEO 113 -PVP 44 -PS 97 Dispersing the single micelle super structure into 0.5 mL ethanol solution, and then adding 1.5 mL deionized water to form a uniformly dispersed solution; then adding 2 mg bis (2-hydroxyethyl) aminotri (hydroxymethyl) methane buffer solution into the solution, and continuously stirring until a homogeneous solution is formed; the homogeneous solution was transferred to a round bottom flask and 5 mg polydopamine was added; then placing the mixture in an oil bath reaction device, wherein the oil bath reaction time is 5-7 h, and the reactions are all carried out at normal temperature; centrifuging, washing and drying to obtain SiO coated with polydopamine 2 @PEO 113 -PVP 44 -PS 97 The composite particles of the single micelle have centrifugal rotation speed of 8000-15000 r/min, washing condition of 95% ethanol solution, washing times of 2-6 times, drying temperature of 50-80 ℃ and drying time of 20-30 h;
s3, carbonizing dopamine and removing a template: roasting the composite particles in nitrogen atmosphere to obtain SiO 2 A @ mesoporous carbon superstructure; treating with hydrofluoric acid aqueous solution, and removing the silicon dioxide template to obtain raspberry-shaped mesoporous carbon spheres with high specific surface; roasting is divided into two stages, wherein the roasting temperature in the first stage is 300-400 DEG CRoasting for 1-3h at 600-900 ℃ in the second stage and 2-4 h; the volume percentage of the hydrofluoric acid aqueous solution is 3-8%, and the acid treatment time is 20-30 h.
3. The raspberry-shaped mesoporous carbon sphere with the high specific surface is characterized in that the mesoporous carbon sphere is of a hollow structure, a shell layer is provided with a mesoporous super structure and an open broken hole, the particle size of the mesoporous carbon sphere is 300-400nm, and the number of the super structure protrusions on the mesoporous carbon sphere is 70-360; the preparation method comprises the following steps:
s1, preparing a super-structure soft and hard double template: siO to be prepared by St method 2 Dispersing the nanospheres with ethanol to form a 1.0 mg/mL homogeneous alcoholic solution; 20 mg PEO 113 -PVP 98 -PS 142 The single micelle is dispersed in 10 mL glacial acetic acid to form single micelle acetic acid solution; dropwise addition of 2 mL single micelle acetic acid solution to SiO 2 The nanospheres are in homogeneous phase solution; adding 25 mu L ammonia water in 5 min ultrasonic treatment, magnetically stirring to react at 300-600 r/min for 0.5-2 h, centrifuging, washing and drying to obtain SiO 2 @ PEO 113 -PVP 98 -PS 142 A single micelle super structure template; wherein PVP is poly (4-vinylpyridine);
s2, dopamine cladding template: 1mg of SiO 2 @ PEO 113 -PVP 98 -PS 142 Dispersing the single micelle super structure into 0.5 mL ethanol solution, and then adding 1.5 mL deionized water to form a uniformly dispersed solution; then adding 2 mg bis (2-hydroxyethyl) aminotri (hydroxymethyl) methane buffer solution into the solution, and continuously stirring until a homogeneous solution is formed; the homogeneous solution was transferred to a round bottom flask and 5 mg polydopamine was added; then placing the mixture in an oil bath reaction device, wherein the oil bath reaction time is 5-7 h, and the reactions are all carried out at normal temperature; centrifuging, washing and drying to obtain SiO coated with polydopamine 2 @ PEO 113 -PVP 98 -PS 142 The composite particles of single micelle have centrifugal speed of 8000-15000 r/min, washing condition of 95% ethanol solution, washing times of 2-6 times, drying temperature of 50-80deg.C, and dryingThe time is 20-30 h;
s3, carbonizing dopamine and removing a template: roasting the composite particles in nitrogen atmosphere to obtain SiO 2 A @ mesoporous carbon superstructure; treating with hydrofluoric acid aqueous solution, and removing the silicon dioxide template to obtain raspberry-shaped mesoporous carbon spheres with high specific surface; roasting is divided into two stages, wherein the roasting temperature in the first stage is 300-400 ℃, the roasting time is 1-3h, the roasting temperature in the second stage is 600-900 ℃, and the roasting time is 2-4 h; the volume percentage of the hydrofluoric acid aqueous solution is 3-8%, and the acid treatment time is 20-30 h.
4. The method for preparing the raspberry-like mesoporous carbon sphere with high specific surface area according to claim 3, comprising the following steps:
s1, preparing a super-structure soft and hard double template: siO to be prepared by St method 2 Dispersing the nanospheres with ethanol to form a 1.0 mg/mL homogeneous alcoholic solution; 20 mg PEO 113 -PVP 98 -PS 142 The single micelle is dispersed in 10 mL glacial acetic acid to form single micelle acetic acid solution; dropwise addition of 2 mL single micelle acetic acid solution to SiO 2 The nanospheres are in homogeneous phase solution; adding 25 mu L ammonia water in 5 min ultrasonic treatment, magnetically stirring to react at 300-600 r/min for 0.5-2 h, centrifuging, washing and drying to obtain SiO 2 @ PEO 113 -PVP 98 -PS 142 A single micelle super structure template; wherein PVP is poly (4-vinylpyridine);
s2, dopamine cladding template: 1mg of SiO 2 @ PEO 113 -PVP 98 -PS 142 Dispersing the single micelle super structure into 0.5 mL ethanol solution, and then adding 1.5 mL deionized water to form a uniformly dispersed solution; then adding 2 mg bis (2-hydroxyethyl) aminotri (hydroxymethyl) methane buffer solution into the solution, and continuously stirring until a homogeneous solution is formed; the homogeneous solution was transferred to a round bottom flask and 5 mg polydopamine was added; then placing the mixture in an oil bath reaction device, wherein the oil bath reaction time is 5-7 h, and the reactions are all carried out at normal temperature; centrifuging, washing and drying to obtain SiO coated with polydopamine 2 @ PEO 113 -PVP 98 -PS 142 The composite particles of the single micelle have centrifugal rotation speed of 8000-15000 r/min, washing condition of 95% ethanol solution, washing times of 2-6 times, drying temperature of 50-80 ℃ and drying time of 20-30 h;
s3, carbonizing dopamine and removing a template: roasting the composite particles in nitrogen atmosphere to obtain SiO 2 A @ mesoporous carbon superstructure; treating with hydrofluoric acid aqueous solution, and removing the silicon dioxide template to obtain raspberry-shaped mesoporous carbon spheres with high specific surface; roasting is divided into two stages, wherein the roasting temperature in the first stage is 300-400 ℃, the roasting time is 1-3h, the roasting temperature in the second stage is 600-900 ℃, and the roasting time is 2-4 h; the volume percentage of the hydrofluoric acid aqueous solution is 3-8%, and the acid treatment time is 20-30 h.
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