CN101177253A - Method for preparing hollow micrometre carbon ball with structured size - Google Patents
Method for preparing hollow micrometre carbon ball with structured size Download PDFInfo
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- CN101177253A CN101177253A CNA200610114339XA CN200610114339A CN101177253A CN 101177253 A CN101177253 A CN 101177253A CN A200610114339X A CNA200610114339X A CN A200610114339XA CN 200610114339 A CN200610114339 A CN 200610114339A CN 101177253 A CN101177253 A CN 101177253A
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- polystyrene
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- conduction high
- ball
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- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 16
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 14
- 238000000034 method Methods 0.000 title claims description 13
- 239000004793 Polystyrene Substances 0.000 claims abstract description 58
- 229920002223 polystyrene Polymers 0.000 claims abstract description 58
- 239000000178 monomer Substances 0.000 claims abstract description 37
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims abstract description 26
- 238000002360 preparation method Methods 0.000 claims abstract description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000008367 deionised water Substances 0.000 claims abstract description 13
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 13
- 239000013067 intermediate product Substances 0.000 claims abstract description 13
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims abstract description 13
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000007800 oxidant agent Substances 0.000 claims abstract description 10
- 239000000047 product Substances 0.000 claims abstract description 8
- 229910052573 porcelain Inorganic materials 0.000 claims abstract description 6
- 238000010438 heat treatment Methods 0.000 claims abstract description 4
- 229920000642 polymer Polymers 0.000 claims description 26
- 239000000243 solution Substances 0.000 claims description 22
- 241000143432 Daldinia concentrica Species 0.000 claims description 16
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical group C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 15
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 14
- 239000012298 atmosphere Substances 0.000 claims description 13
- LCPVQAHEFVXVKT-UHFFFAOYSA-N 2-(2,4-difluorophenoxy)pyridin-3-amine Chemical compound NC1=CC=CN=C1OC1=CC=C(F)C=C1F LCPVQAHEFVXVKT-UHFFFAOYSA-N 0.000 claims description 12
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 claims description 12
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 claims description 10
- 239000007864 aqueous solution Substances 0.000 claims description 10
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N N-phenyl amine Natural products NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims description 8
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 8
- 238000007669 thermal treatment Methods 0.000 claims description 8
- 238000010907 mechanical stirring Methods 0.000 claims description 6
- 239000000725 suspension Substances 0.000 claims description 6
- 238000013019 agitation Methods 0.000 claims description 5
- 238000004140 cleaning Methods 0.000 claims description 5
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 5
- 229930192474 thiophene Natural products 0.000 claims description 5
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 4
- 238000000151 deposition Methods 0.000 claims description 3
- 230000008021 deposition Effects 0.000 claims description 3
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 3
- 125000002490 anilino group Chemical group [H]N(*)C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 claims description 2
- 150000003233 pyrroles Chemical class 0.000 claims description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 abstract description 4
- 229910052757 nitrogen Inorganic materials 0.000 abstract description 2
- 239000002775 capsule Substances 0.000 abstract 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 abstract 1
- 239000005977 Ethylene Substances 0.000 abstract 1
- 239000003054 catalyst Substances 0.000 abstract 1
- 238000001816 cooling Methods 0.000 abstract 1
- 230000007935 neutral effect Effects 0.000 abstract 1
- 230000001590 oxidative effect Effects 0.000 abstract 1
- 239000002994 raw material Substances 0.000 abstract 1
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 description 6
- 229920000767 polyaniline Polymers 0.000 description 4
- 229920000128 polypyrrole Polymers 0.000 description 4
- 229920000123 polythiophene Polymers 0.000 description 4
- 239000003575 carbonaceous material Substances 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000004005 microsphere Substances 0.000 description 3
- 238000005303 weighing Methods 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 2
- 150000001722 carbon compounds Chemical class 0.000 description 1
- 238000010531 catalytic reduction reaction Methods 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
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Abstract
The invention relates to a preparation method for hollow micron carbon capsule, which is characterized in that a polystyrene microballoon sphere is added into the water, the solution with a polystyrene microballoon sphere is dispersed by ultrasonic, so the conductive superpolymer monomer is added into the solution with the ethylene microballoon sphere, and then is mixed round and dispersed to form a mixed system; the oxidant solution is slowly dripped into the mixed system to get an intermediate product after 3 to 6 hours; the intermediate product is washed to be neutral by deionized water, and then a conductive superpolymer-polystyrene sphere is obtained after the intermediate product is cleaned with ethanol and dried in the air; the conductive superpolymer-polystyrene sphere is soaked into tetrahydrofuran and is centrifugal after 10 to 40 hours, thereby the hollow conductive superpolymer-polystyrene sphere is obtained after dried at a temperature of 50 DEG C to 80 DEG C; then the hollow conductive superpolymer-polystyrene sphere is arranged into a porcelain boat, after the vacuum heat treatment for 1.5 to 4.5 hours under the nitrogen, a hollow carbon capsule with regular size through natural cooling to ambient temperature. The invention has the advantages of low cost for raw material, heat treatment under the condition of air without catalyst, and regular size of the product.
Description
Invention field
The present invention relates to a kind of preparation method of hollow carbon micron-spheres of simple efficient production structured size.
Background technology
Carbon material is the important materials closely bound up with the human civilization progress, and the carbon simple substance and the carbon compound of various different shapes have been made huge contribution in human development.In recent years spherical carbon material because its in biological field and electronic applications wide application prospect and caused the great interest of people.The carbon material of ball-like structure synthetic has chemical vapour deposition, plasma-deposited, catalyse pyrolysis, catalytic reduction method and arc process etc. at present.And the most widely used preparation method is an arc process.This method is at high temperature carried out arc-over reaction with pulsed current, press in needing one to be the atmospheric reaction chamber of 1-10, and the product that obtains needs a purge process.
Summary of the invention
The objective of the invention is to: a kind of preparation method of hollow carbon micron-spheres of advantages of simplicity and high efficiency structured size is provided, and the material cost of this method is cheap, does not need catalyzer, products made thereby structured size under the thermal treatment air conditions.
Technical scheme of the present invention is as follows:
The invention provides the preparation method of the hollow carbon micron-spheres of structured size, it is characterized in that: the regular polystyrene micron ball of preparation size at first, under the polystyrene spheres existence condition, prepare conduction high polymer-polystyrene spheres that conduction high polymer evenly coats then, thereby obtain the conduction high polymer ball of hollow again by the polystyrene in tetrahydrofuran (THF) flush away conduction high polymer-polystyrene spheres, at last by at a certain temperature the conduction high polymer ball being heat-treated the hollow carbon balls that obtains structured size.Described hollow carbon balls diameter is between 200-400nm, and wall thickness is between 10-50nm.
Its concrete steps are as follows;
1) preparation of hollow conduction high polymer ball;
A, add the ratio of 1 gram polystyrene micron ball, polystyrene micron ball is added in the entry the ultrasonic aqueous solution that made it fully disperse to obtain being dispersed with polystyrene micron ball in 30 minutes in every 50ml water;
B, the conduction high polymer monomer added be dispersed with in the aqueous solution of polystyrene micron ball, fully disperse under the magnetic agitation condition, obtain conduction high polymer monomer/polystyrene micron ball mixed system;
The mass ratio of described conduction high polymer monomer and polystyrene micron ball is 0.5-3;
C, oxidizing agent solution slowly is added drop-wise in conduction high polymer monomer/polystyrene micron ball mixed system with certain drop rate, drips and finish afterreaction and continue 3-6h and obtain intermediate product;
Described oxidizing agent solution is iron trichloride or ammonium persulfate solution;
Described oxidizing agent solution concentration is 0.7-1.5M;
The drop rate of described oxidizing agent solution is 7-20ml/h;
Described oxygenant and conduction high polymer monomer mole ratio are 1-4;
D, intermediate product earlier is washed till neutrality with deionized water, and then after cleaning with ethanol, 50-80 ℃ of dry 6-10h under the air atmosphere obtains conduction high polymer-polystyrene spheres that conduction high polymer evenly coats;
E, conduction high polymer-polystyrene spheres that conduction high polymer is evenly coated are soaked in 10-40h in the tetrahydrofuran (THF), and then through centrifugal, 50-80 ℃ of dry 6-10h under air atmosphere obtains hollow conduction high polymer ball with centrifugal back products therefrom;
2) the hollow conduction high polymer ball that obtains is placed porcelain boat, under nitrogen atmosphere, behind the vacuum heat treatment 1.5-4.5h, naturally cool to room temperature again, promptly obtain the hollow carbon micron-spheres that diameter is the structured size of 10-50nm for the 200-400nm wall thickness.
Being prepared as follows of described polystyrene micron ball used in the present invention:
A, styrene monomer and methacrylic acid monomer are dissolved in the deionized water, under mechanical stirring, fully disperse, obtain containing the mixed system of styrene monomer and methacrylic acid monomer;
The volume ratio of described styrene monomer, methacrylic acid monomer and deionized water is 18: 2: 140;
B, Sodium Persulfate fully is dissolved in the deionized water, obtaining concentration is the Sodium Persulfate solution of 0.04M;
C, Sodium Persulfate solution add and contain in the mixed system of styrene monomer and methacrylic acid monomer, and mechanical stirring is after 20 minutes, reheat to 80 ℃, and 80 ℃ continue 12h down, obtain white suspension;
Described Sodium Persulfate solution is 1: 8 with the volume ratio that contains the mixed system of styrene monomer and methacrylic acid monomer;
D, centrifugal white suspension, the white depositions 60 ℃ of dry 12h under air atmosphere with obtaining after centrifugal obtain 200nm-400nm polystyrene micron ball.
Described conduction high polymer monomer is aniline, pyrroles or thiophene.
Described 2) thermal treatment temp is 750-1100 ℃ in.
Compared with prior art, the method for preparing hollow carbon balls provided by the invention has following advantage:
1, hollow carbon balls purity height provided by the invention, good dispersity, structured size is in the 200-400nm scope;
2, the required material cost of preparation method provided by the invention is cheap;
3, preparation method provided by the invention does not need special conversion unit, does not need catalyzer during thermal treatment;
4, whole process of preparation provided by the invention is removed outside the last thermal treatment, all carries out under air conditions, need not nitrogen protection;
5, preparation method provided by the invention can be simply by the monomeric amount of conduction high polymer that adds just can different wall hollow carbon balls.
Description of drawings
Fig. 1 and Fig. 1 are scanning electron microscope (SEM) photo and X-ray energy spectrum (EDX) analytical results of the hollow carbon balls for preparing;
Wherein: the SEM figure of Fig. 1-hollow carbon balls;
The EDX figure of Fig. 2-hollow carbon balls.
Embodiment
1) preparation of polystyrene microsphere
A, 18 parts of styrene monomers and 2 parts of methacrylic acid monomers are dissolved in 140 parts of deionized waters, under mechanical stirring, fully disperse, obtain containing the mixed system of styrene monomer and methacrylic acid monomer;
B, Sodium Persulfate fully is dissolved in the deionized water, obtaining concentration is the Sodium Persulfate solution of 0.04M;
C, be that the Sodium Persulfate solution of 0.04M adds and to contain in the mixed system of styrene monomer and methacrylic acid monomer with 20ml concentration, mechanical stirring is after 20 minutes, reheat to 80 ℃, and 80 ℃ continue 12h down, obtain white suspension; Described Sodium Persulfate solution is 1: 8 with the volume ratio that contains the mixed system of styrene monomer and methacrylic acid monomer;
D, centrifugal white suspension, the white depositions 60 ℃ of dry 12h under air atmosphere with obtaining after centrifugal obtain 200nm-400nm polystyrene micron ball.
2) preparation hollow polypyrrole ball;
A, take by weighing the 1g polystyrene spheres in 50ml water, the ultrasonic aqueous solution that made it fully disperse to obtain being dispersed with polystyrene micron ball in 30 minutes;
B, the pyrrole monomer of measuring 0.5ml join in the aqueous solution that is dispersed with polystyrene micron ball, fully disperse under the magnetic agitation condition, obtain pyrrole monomer/polystyrene micron ball mixed system;
C, be that the liquor ferri trichloridi of 0.7M slowly is added drop-wise in pyrrole monomer/polystyrene micron ball mixed system with the drop rate of 7ml/h with 10.3ml concentration, drip and finish afterreaction and continue 3h and obtain intermediate product;
D, intermediate product earlier is washed till neutrality with deionized water, and then after cleaning with ethanol, the following 50 ℃ of dry 6h of air atmosphere obtain polypyrrole-polystyrene spheres that polypyrrole evenly coats;
E, polypyrrole-polystyrene spheres is soaked in 10h in the tetrahydrofuran (THF), then through centrifugal, 50 ℃ of dry 6h under air atmosphere obtain hollow polypyrrole ball with centrifugal back products therefrom;
3) the hollow polypyrrole ball that obtains is placed porcelain boat, under nitrogen atmosphere, behind 930 ℃ of thermal treatment 1.5h of vacuum, make it naturally cool to room temperature and promptly obtain the hollow carbon micron-spheres that diameter is the structured size of 15nm for the 200-400nm wall thickness.
Scanning electron microscope (SEM) photo and X-ray energy spectrum (EDX) analytical results of the hollow carbon balls of the present invention's preparation are seen Figure 1A-B respectively.
1) preparation of 200-400nm polystyrene microsphere is with embodiment 1;
2) preparation of hollow polyaniline ball;
A, take by weighing the 1g polystyrene spheres in 50ml water, the ultrasonic aqueous solution that made it fully disperse to obtain being dispersed with polystyrene micron ball in 30 minutes;
B, the aniline monomer of measuring 2ml join in the aqueous solution that is dispersed with polystyrene micron ball, fully disperse under the magnetic agitation condition, obtain aniline monomer/polystyrene micron ball mixed system;
C, to be the 1.1M ammonium persulfate solution with 50ml concentration slowly be added drop-wise in aniline monomer/polystyrene micron ball mixed system with the drop rate of 14ml/h, drips to finish afterreaction and continue 4.5h and obtain intermediate product;
D, intermediate product earlier is washed till neutrality with deionized water, and then after cleaning with ethanol, the following 65 ℃ of dry 8h of air atmosphere obtain polyaniline-polystyrene spheres that polyaniline evenly coats;
E, polyaniline-polystyrene spheres is soaked in 25h in the tetrahydrofuran (THF), then through centrifugal, 65 ℃ of dry 8zh under air atmosphere obtain hollow polyaniline ball with centrifugal back products therefrom;
3) the hollow polyaniline ball that obtains is placed porcelain boat, under nitrogen atmosphere, behind 750 ℃ of thermal treatment 2h of vacuum, make it naturally cool to room temperature and promptly obtain the hollow carbon micron-spheres that diameter is the structured size of 35nm for the 200-400nm wall thickness.
1) preparation of 200-400nm polystyrene microsphere is with embodiment 1;
2) preparation of hollow Polythiophene ball;
A, take by weighing the 1g polystyrene spheres in 50ml water, the ultrasonic aqueous solution that made it fully disperse to obtain being dispersed with polystyrene micron ball in 30 minutes;
B, the thiophene monomer of measuring 2.85ml join in the aqueous solution that is dispersed with polystyrene micron ball, fully disperse under the magnetic agitation condition, obtain thiophene monomer/polystyrene micron ball mixed system;
C, to be the 1.5M liquor ferri trichloridi with 94.4ml concentration slowly be added drop-wise in thiophene monomer/polystyrene micron ball mixed system with the drop rate of 20ml/h, drips to finish afterreaction and continue 6h and obtain intermediate product;
D, intermediate product earlier is washed till neutrality with deionized water, and then after cleaning with ethanol, the following 80 ℃ of dry 10h of air atmosphere obtain Polythiophene-polystyrene spheres that Polythiophene evenly coats;
E, Polythiophene-polystyrene spheres is soaked in 40h in the tetrahydrofuran (THF), then through centrifugal, 80 ℃ of dry 10h under air atmosphere obtain hollow Polythiophene ball with centrifugal back products therefrom;
3) the hollow Polythiophene ball that obtains is placed porcelain boat, under nitrogen atmosphere, behind 1100 ℃ of thermal treatment 4.5h of vacuum, make it naturally cool to room temperature and promptly obtain the hollow carbon micron-spheres that diameter is the structured size of 50nm for the 200-400nm wall thickness.
Claims (5)
1. the preparation method of the hollow carbon micron-spheres of a structured size, its concrete steps are as follows:
1) preparation of hollow conduction high polymer ball;
A, add the ratio of 1 gram polystyrene micron ball, polystyrene micron ball is added in the entry the ultrasonic aqueous solution that made it fully disperse to obtain being dispersed with polystyrene micron ball in 30 minutes in every 50ml water;
B, the conduction high polymer monomer added be dispersed with in the aqueous solution of polystyrene micron ball, fully disperse under the magnetic agitation condition, obtain conduction high polymer monomer/polystyrene micron ball mixed system;
The mass ratio of described conduction high polymer monomer and polystyrene micron ball is 0.5-3;
C, oxidizing agent solution slowly is added drop-wise in conduction high polymer monomer/polystyrene micron ball mixed system with certain drop rate, drips and finish afterreaction and continue 3-6h and obtain intermediate product;
Described oxidizing agent solution is iron trichloride or ammonium persulfate solution;
Described oxidizing agent solution concentration is 0.7-1.5M;
The drop rate of described oxidizing agent solution is 7-20ml/h;
Described oxygenant and conduction high polymer monomer mole ratio are 1-4;
D, intermediate product earlier is washed till neutrality with deionized water, and then after cleaning with ethanol, 50-80 ℃ of dry 6-10h under the air atmosphere obtains conduction high polymer-polystyrene spheres that conduction high polymer evenly coats;
E, conduction high polymer-polystyrene spheres that conduction high polymer is evenly coated are soaked in 10-40h in the tetrahydrofuran (THF), and then through centrifugal, 50-80 ℃ of dry 6-10h under air atmosphere obtains hollow conduction high polymer ball with centrifugal back products therefrom;
2) the hollow conduction high polymer ball that obtains is placed porcelain boat, under nitrogen atmosphere, behind the vacuum heat treatment 1.5-4.5h, naturally cool to room temperature again, promptly obtain the hollow carbon micron-spheres that diameter is the structured size of 10-50nm for the 200-400nm wall thickness.
2. by the method for preparing hollow carbon balls of the described structured size of claim 1, it is characterized in that being prepared as follows of described polystyrene micron ball:
A, styrene monomer and methacrylic acid monomer are dissolved in the deionized water, under mechanical stirring, fully disperse, obtain containing the mixed system of styrene monomer and methacrylic acid monomer;
The volume ratio of described styrene monomer, methacrylic acid monomer and deionized water is 18: 2: 140;
B, Sodium Persulfate fully is dissolved in the deionized water, obtaining concentration is the Sodium Persulfate solution of 0.04M;
C, Sodium Persulfate solution added contain in the mixed system of styrene monomer and methacrylic acid monomer, mechanical stirring is after 20 minutes, reheat to 80 ℃, and 80 ℃ continue 12h down, obtain white suspension;
Described Sodium Persulfate solution is 1: 8 with the volume ratio that contains the mixed system of styrene monomer and methacrylic acid monomer;
D, centrifugal white suspension, the white depositions 60 ℃ of dry 12h under air atmosphere with obtaining after centrifugal obtain polystyrene micron ball.
3. by the method for preparing hollow carbon balls of the described structured size of claim 1, it is characterized in that described conduction high polymer monomer is aniline, pyrroles or thiophene.
4. by the method for preparing hollow carbon balls of the described structured size of claim 1, it is characterized in that described step 2) in oxidizing agent solution refer to iron trichloride and ammonium persulfate solution;
5. by the method for preparing hollow carbon balls of the described structured size of claim 1, it is characterized in that described step 2) in thermal treatment temp be 750-1100 ℃.
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| CNB200610114339XA CN100537422C (en) | 2006-11-07 | 2006-11-07 | Method for preparing hollow micrometre carbon ball with structured size |
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| CN102020269A (en) * | 2011-01-07 | 2011-04-20 | 中国科学院化学研究所 | Hollow carbon sphere and preparation method thereof |
| CN102344552A (en) * | 2010-08-02 | 2012-02-08 | 中国科学院理化技术研究所 | Preparation method of three-dimensional chrysanthemum-shaped poly (3, 4-ethylenedioxythiophene) nanostructural material |
| CN102391510A (en) * | 2011-07-13 | 2012-03-28 | 扬州大学 | Production method for synthesizing polypyrrole hollow spheres by self template process |
| CN103848413A (en) * | 2012-12-05 | 2014-06-11 | 中国科学院上海硅酸盐研究所 | Preparation method of mesoporous carbon sphere material |
| CN105712317A (en) * | 2016-01-30 | 2016-06-29 | 山西大学 | Preparation method of nano-contained hollow carbon material |
| CN106276843A (en) * | 2015-05-12 | 2017-01-04 | 北京化工大学 | A kind of method preparing monodisperse hollow carbon microspheres |
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| CN102344552B (en) * | 2010-08-02 | 2012-10-03 | 中国科学院理化技术研究所 | Preparation method of three-dimensional chrysanthemum-shaped poly (3, 4-ethylenedioxythiophene) nanostructural material |
| CN102020269A (en) * | 2011-01-07 | 2011-04-20 | 中国科学院化学研究所 | Hollow carbon sphere and preparation method thereof |
| CN102020269B (en) * | 2011-01-07 | 2013-05-29 | 中国科学院化学研究所 | Hollow carbon sphere and preparation method thereof |
| CN102391510A (en) * | 2011-07-13 | 2012-03-28 | 扬州大学 | Production method for synthesizing polypyrrole hollow spheres by self template process |
| CN102391510B (en) * | 2011-07-13 | 2012-12-26 | 扬州大学 | Production method for synthesizing polypyrrole hollow spheres by self template process |
| CN103848413B (en) * | 2012-12-05 | 2016-08-10 | 中国科学院上海硅酸盐研究所 | A kind of preparation method of mesoporous carbon spheres material |
| CN103848413A (en) * | 2012-12-05 | 2014-06-11 | 中国科学院上海硅酸盐研究所 | Preparation method of mesoporous carbon sphere material |
| CN106276843A (en) * | 2015-05-12 | 2017-01-04 | 北京化工大学 | A kind of method preparing monodisperse hollow carbon microspheres |
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| CN110482521A (en) * | 2019-07-24 | 2019-11-22 | 厦门大学 | A kind of preparation method of hollow carbon balls |
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| CN111540614A (en) * | 2020-06-03 | 2020-08-14 | 梁二波 | Nitrogen-doped porous carbon hollow sphere supercapacitor electrode active material and preparation method thereof |
| CN113083305A (en) * | 2021-03-12 | 2021-07-09 | 北京化工大学常州先进材料研究院 | Fe-doped hollow core-shell carbon sphere electrocatalyst material and preparation method thereof |
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