CN107673323A - A kind of method that self-template prepares hollow carbon balls - Google Patents
A kind of method that self-template prepares hollow carbon balls Download PDFInfo
- Publication number
- CN107673323A CN107673323A CN201711164047.1A CN201711164047A CN107673323A CN 107673323 A CN107673323 A CN 107673323A CN 201711164047 A CN201711164047 A CN 201711164047A CN 107673323 A CN107673323 A CN 107673323A
- Authority
- CN
- China
- Prior art keywords
- hollow carbon
- carbon balls
- self
- template
- template according
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Landscapes
- Carbon And Carbon Compounds (AREA)
Abstract
The present invention provides a kind of method that self-template prepares hollow carbon balls：Hexachlorocyclotriph,sphazene and comonomer are scattered in organic solvent, then add acid binding agent, is reacted 2 ~ 6 hours under the conditions of ultrasonic wave added, after reaction terminates, through centrifuging, washing, obtains solid polyphosphazene microspheres；The polyphosphazene microspheres of gained are moved in retort, under inert gas shielding, hollow carbon balls are obtained after high-temperature calcination.The inventive method realizes the hollow carbon balls that self-template method quickly prepares good monodispersity, uniform particle diameter, wall thickness and size tunable.Whole preparation process is not required to additional template, and preparation method is simple, environment-friendly, is easy to largely produce.
Description
Technical field
The present invention relates to field of material preparation, and in particular to a kind of method that self-template prepares hollow carbon balls.
Background technology
Carbon micro Nano material has the characteristics that hole is abundant, specific surface area is high, stability is good, thus catalysis, adsorb with
And the energy storage such as ultracapacitor, lithium ion battery field has broad application prospects, and attracts the research of scientific research personnel always
Interest.Particularly hollow carbon balls, it has unique cavity structure and higher specific surface area, thus the preparation of hollow carbon balls
And application attracts the extensive concern of people.
At present, the method that a variety of preparation hollow carbon balls have been developed in people, such as chemical vapour deposition technique, hydro-thermal method and mould
Plate method etc., particularly template, hollow carbon balls are prepared frequently as extensive method.Its mainly using silica, polystyrene,
The rigid particles such as calcium carbonate, or the flexible structure such as microemulsion micella, supermolecule micella prepare spherical template, are then wrapped on its surface
Carbon matrix precursor is covered, most removes template through the methods of high-temperature calcination, etching afterwards.[S. Li, A. Pasc, V. Fierroa and
A. Celzard. Hollow carbon spheres, synthesis and applications. J. Mater.
Chem. A, 2016,4,12686] patent CN106563483 and CN106986325A are with SiO2Microballoon is hard template
To prepare hollow carbon balls, and removing template is removed by etching agent of HF.During above-mentioned template prepares hollow carbon balls, the preparation of template
Substantial amounts of toxic reagent and catalyst are often needed, and to improve the dispersiveness of template, needs to add substantial amounts of surfactant or right more
Its surface is modified, in addition, the removal of segment template need to often use hydrofluoric acid, sodium hydroxide, hydrochloric acid, tetrahydrofuran etc. strong rotten
Corrosion and toxic reagent carry out chemical removal.Not only step is various for these steps, a large amount of noxious materials is also introduced, easily to people
Body and environment damage.
The content of the invention
The present invention proposes a kind of method that self-template prepares hollow carbon balls, solves prior art and needs to use poisonous examination
Agent and catalyst, and need add exhibiting high surface activating agent the problem of.
To solve the above problems, the present invention uses following technical scheme：A kind of method that self-template prepares hollow carbon balls, step
It is rapid as follows：
（1）Hexachlorocyclotriph,sphazene and comonomer are scattered in organic solvent at room temperature；Then acid binding agent is added, in 20~30
The h of ultrasonic reaction 2~6, obtains reaction solution under the conditions of DEG C；
（2）By step（1）In reaction solution centrifuge, washed using ethanol and deionized water, be dried in vacuo after washing afterwards
Obtain solid polyphosphazene microspheres；
（3）By step（2）In obtained solid polyphosphazene microspheres be placed in retort, be passed through nitrogen or argon gas 1h, afterwards high temperature
Sintering obtains hollow carbon balls.
The step（1）Middle hexachlorocyclotriph,sphazene, comonomer, the mass ratio of organic solvent and acid binding agent are（4-50）：
（3-60）：（3000-6000）：（50-140）.
The step（1）Middle comonomer be phloroglucin, hydroquinones, resorcinol, p-phenylenediamine, melamine,
4,4 '-dioxydiphenyl methane, 4,4 '-dihydroxydiphenylsulisomer, 4,4' diaminodiphenyl sulfone, 4,4 '-MDA or
Any one in 4,4 '-diaminodiphenyl ether.
The step（1）Middle organic solvent is in ethanol, propyl alcohol, acetonitrile, acetone, tetrahydrofuran, toluene or n-hexane
It is at least one.
The step（1）Acid binding agent is any in triethylamine, tripropyl amine (TPA), tri-n-butylamine, triamylamine, sodium carbonate or potassium carbonate
It is a kind of.
The step（1）Middle ultrasonic power is 100~240 W, and supersonic frequency is 40-80 kHz.
The step（2）In vacuum drying temperature be 50-80 DEG C, drying time 10-24h.
The step（3）In be passed through nitrogen or argon gas 1h after, 550-600 is warming up to 1~20 DEG C/min heating rate
DEG C 2 h of insulation, are heated up 700~1000 DEG C with 1~20 DEG C/min heating rate, are incubated 2-10 h, naturally cool to afterwards
Room temperature obtains hollow carbon balls.
The step（3）The particle diameter of hollow carbon balls is 450~560 nm.
The beneficial effects of the invention are as follows：Preparation technology of the present invention is simple, and raw material sources enrich, and is easy to batch and prepares, carbon ball
The solid polyphosphazene microspheres of precursor have the functional groups such as substantial amounts of hydroxyl, amino, have well in ethanol, acetone equal solvent
Dispersiveness, while any surfactant or synergist is not used, locates after simplifying without additional template is introduced in preparation process
Manage program；By controlling solvent or acid binding agent type to realize the particle diameter of solid polyphosphazene microspheres in the range of 600~850 nm
It is adjustable, and then realize the size tunable of hollow carbon balls；The big I of specific surface area and pore volume of products obtained therefrom hollow carbon balls passes through carbon
Chemical industry skill is controlled, and such as can control the effusion process of non-carbon components in polyphosphazene microspheres by regulating and controlling heating rate, and then
Regulate and control product hollow carbon balls in mesoporous pore size distribution, finally realize its specific surface area, pore volume size it is controllable；In products obtained therefrom
The monodispersity of empty carbon ball is good, size uniformity, and there is obvious cavity structure and abundant meso-hole structure, mesoporous pore size mainly to divide
Cloth is in 2~10 nm.The hollow carbon balls obtained by the use of the preparation method can be applied to CO as adsorbent2In terms of capture, meanwhile,
It can be used as the electrode material of the energy storage devices such as catalyst carrier, sorbing material and ultracapacitor or lithium ion battery.
Brief description of the drawings
In order to illustrate more clearly about the embodiment of the present invention or technical scheme of the prior art, below will be to embodiment or existing
There is the required accompanying drawing used in technology description to be briefly described, it should be apparent that, drawings in the following description are only this
Some embodiments of invention, for those of ordinary skill in the art, on the premise of not paying creative work, can be with
Other accompanying drawings are obtained according to these accompanying drawings.
Fig. 1 is the stereoscan photograph of the solid polyphosphazene microspheres prepared by embodiment 1.
Fig. 2 is the transmission electron microscope photo of the solid polyphosphazene microspheres prepared by embodiment 1.
Fig. 3 is the stereoscan photograph of the hollow carbon balls prepared by embodiment 1.
Fig. 4 is the transmission electron microscope photo of the hollow carbon balls prepared by embodiment 1.
Fig. 5 is the pore-size distribution of the hollow carbon balls prepared by embodiment 1.
Embodiment
Below in conjunction with the embodiment of the present invention, technical scheme is clearly and completely described, it is clear that institute
The embodiment of description is only part of the embodiment of the present invention, rather than whole embodiments.Based on the embodiment in the present invention,
The every other embodiment that those of ordinary skill in the art are obtained under the premise of creative work is not paid, belongs to this hair
The scope of bright protection.
Embodiment 1
In the flask that 250 mL are dried, 100 mL acetonitriles are added, are weighed between 0.12 g hexachlorocyclotriph,sphazenes and 0.09 g
Benzenetriol, 1 g triethylamines are added thereto after well mixed, immediately sealed flask, in ultrasonic cleaner under the conditions of 30 DEG C
（150 W, 40 kHz）Reacted 2 hours in water-bath.Reaction centrifuges after terminating, and washs centrifugation with ethanol and deionized water respectively
Product 3~4 times, finally product is dried in vacuo 24 hours under the conditions of 60 DEG C, obtains solid polyphosphazene microspheres.
Obtained solid polyphosphazene microspheres are placed in porcelain boat and delivered in retort, first leads to inert gas and drives away charcoal in 1 hour
Change the air in stove, be then to slowly warm up to 600 DEG C with 1 DEG C/min heating rate, be incubated 2 hours, then proceed to heat up
To 900 DEG C, insulation is naturally cooling to room temperature after 3 hours, obtains being rich in mesoporous hollow carbon balls.Characterization result shows prepared
The average grain diameters of hollow carbon balls be 500 nm, specific surface area is 2257 m2/ g, aperture are mainly distributed on the mesoporous of 2~10 nm
Scope.
Fig. 1 shows the stereoscan photograph of the solid polyphosphazene microspheres prepared under the conditions of embodiment 1, the results showed that institute
The solid polyphosphazene microspheres average diameter prepared is 820 nm, favorable dispersibility.
Fig. 2 shows the projection electromicroscopic photograph of the solid polyphosphazene microspheres prepared under the conditions of embodiment 1, the results showed that institute
The polyphosphazene microspheres of preparation are solid microsphere, and surface is smooth.
Fig. 3 shows the stereoscan photograph of the hollow carbon balls prepared under the conditions of embodiment 1, the results showed that gained is hollow
The average grain diameter of carbon ball is in 500 nm, and monodispersity is good, good sphericity.
Fig. 4 shows the transmission electron microscope photo of the hollow carbon balls prepared under the conditions of embodiment 1, the results showed that gained carbon ball
For hollow carbon balls, monodispersity is good, good sphericity, surface are smooth.
Fig. 5 shows the pore-size distribution of the hollow carbon balls prepared under the conditions of embodiment 1, the results showed that the hole of gained carbon ball
Footpath is mainly distributed on 2~10 nm macropore range.
Embodiment 2
In the flask that 150 mL are dried, 100mL acetonitriles are added, weigh 0.12 g hexachlorocyclotriph,sphazenes and 0.09 g isophthalic
Triphenol, 1 g triethylamines are added thereto after well mixed, immediately sealed flask, in ultrasonic cleaner under the conditions of 30 DEG C
（150 W, 40 kHz）Reacted 1 hour in water-bath.Reaction centrifuges after terminating, and washs centrifugation with ethanol and deionized water respectively
Product 3~4 times, finally product is dried in vacuo 24 hours under the conditions of 60 DEG C, obtains solid polyphosphazene microspheres.
Obtained solid polyphosphazene microspheres are placed in porcelain boat and delivered in retort, first leads to inert gas and drives away charcoal in 1 hour
Change the air in stove, be then to slowly warm up to 600 DEG C with 1 DEG C/min heating rate, be incubated 2 hours, then proceed to heat up
To 850 DEG C, insulation is naturally cooling to room temperature after 3 hours, obtains being rich in mesoporous hollow carbon balls.Characterization result shows prepared
The average grain diameters of hollow carbon balls be 500 nm, specific surface area is 2134 m2/ g, mesoporous model of the pore-size distribution in 2~10 nm
Enclose.
Embodiment 3
In the flask that 150 mL are dried, 100 mL acetonitriles are added, weigh 0.12 g hexachlorocyclotriph,sphazenes and 0.09 g isophthalic three
Phenol, 1 g triethylamines are added thereto after well mixed, immediately sealed flask, in ultrasonic cleaner under the conditions of 30 DEG C（150
W, 40 kHz）Reacted 2 hours in water-bath.Reaction centrifuges after terminating, and washs centrifugation product 3 with ethanol and deionized water respectively
~4 times, finally product is dried in vacuo 24 hours under the conditions of 60 DEG C, obtains solid polyphosphazene microspheres.
Obtained solid polyphosphazene microspheres are placed in porcelain boat and delivered in retort, first leads to inert gas and drives away charcoal in 1 hour
Change the air in stove, be then to slowly warm up to 1 DEG C/min heating rate to 850 DEG C, Temperature fall after being incubated 3 hours
To room temperature, obtain being rich in mesoporous hollow carbon balls.Characterization result shows that the average grain diameter of prepared hollow carbon balls is 500 nm,
Specific surface area is 1985 m2/ g, macropore range of the pore-size distribution in 2~10 nm.
Embodiment 4
In the flask that 150 mL are dried, 30mL ethanol is added, weighs 0.04 g hexachlorocyclotriph,sphazenes and 0.05 g to benzene
Diphenol, 0.5 g tripropyl amine (TPA)s are added thereto after well mixed, immediately sealed flask, in ultrasonic cleaner under the conditions of 20 DEG C
（100 W, 80 kHz）Reacted 6 hours in water-bath.Reaction centrifuges after terminating, and washs centrifugation with ethanol and deionized water respectively
Product 3 times, finally product is dried in vacuo 24 hours under the conditions of 50 DEG C, obtains solid polyphosphazene microspheres.
Obtained solid polyphosphazene microspheres are placed in porcelain boat and delivered in retort, first leads to nitrogen and drives away retort in 1 hour
In air, be then to slowly warm up to 600 DEG C with 1 DEG C/min heating rate, be incubated 0.5 hour, then proceed to 1
DEG C/min is warming up to 700 DEG C, insulation is naturally cooling to room temperature after 10 hours, obtains being rich in mesoporous hollow carbon balls.
Embodiment 5
In the flask that 150 mL are dried, 35mL propyl alcohol is added, weighs 0.1 g hexachlorocyclotriph,sphazenes and 0.2 g resorcinols,
0.8 g tripropyl amine (TPA)s are added thereto after well mixed, immediately sealed flask, in ultrasonic cleaner under the conditions of 25 DEG C（150 W,
60 kHz）Reacted 4 hours in water-bath.Reaction centrifuges after terminating, and washs centrifugation product 4 with ethanol and deionized water respectively
It is secondary, finally product is dried in vacuo 20 hours under the conditions of 60 DEG C, obtains solid polyphosphazene microspheres.
Obtained solid polyphosphazene microspheres are placed in porcelain boat and delivered in retort, first leads to argon gas and drives away retort in 1 hour
In air, be then to slowly warm up to 580 DEG C with 5 DEG C/min heating rate, be incubated 1 hour, then proceed to be warming up to
900 DEG C, insulation is naturally cooling to room temperature after 8 hours, obtains being rich in mesoporous hollow carbon balls.
Embodiment 6
A kind of method that self-template prepares hollow carbon balls, step are as follows：
In the flask that 150 mL are dried, 40mL acetone is added, weighs 0.2 g hexachlorocyclotriph,sphazenes and 0.2g p-phenylenediamine,
0.6 g tri-n-butylamines are added thereto after well mixed, immediately sealed flask, in ultrasonic cleaner under the conditions of 30 DEG C（180 W,
70 kHz）Reacted 5 hours in water-bath.Reaction centrifuges after terminating, and washs centrifugation product 4 with ethanol and deionized water respectively
It is secondary, finally product is dried in vacuo 18 hours under the conditions of 70 DEG C, obtains solid polyphosphazene microspheres.
Obtained solid polyphosphazene microspheres are placed in porcelain boat and delivered in retort, first leads to argon gas and drives away retort in 1 hour
In air, be then to slowly warm up to 550 DEG C with 10 DEG C/min heating rate, be incubated 2 hours, then proceed to be warming up to
800 DEG C, insulation is naturally cooling to room temperature after 5 hours, obtains being rich in mesoporous hollow carbon balls.
Embodiment 7
A kind of method that self-template prepares hollow carbon balls, step are as follows：
In the flask that 150 mL are dried, add 45mL ethanol, weigh 0.35 g hexachlorocyclotriph,sphazenes and 0.35 g 4,4 '-
Diaminodiphenyl ether, 1.1 g potassium carbonate are added thereto after well mixed, immediately sealed flask, in ultrasound under the conditions of 30 DEG C
Ripple washer（200 W, 70 kHz）Reacted 2 hours in water-bath.Reaction centrifuges after terminating, and uses ethanol and deionized water respectively
Product, is finally dried in vacuo 12 hours, obtains solid polyphosphazene microspheres by washing centrifugation product 4 times under the conditions of 65 DEG C.
Obtained solid polyphosphazene microspheres are placed in porcelain boat and delivered in retort, first leads to argon gas and drives away retort in 1 hour
In air, be then to slowly warm up to 590 DEG C with 15 DEG C/min heating rate, be incubated 2 hours, then proceed to be warming up to
950 DEG C, insulation is naturally cooling to room temperature after 9 hours, obtains being rich in mesoporous hollow carbon balls.
Embodiment 8
A kind of method that self-template prepares hollow carbon balls, step are as follows：
In the flask that 150 mL are dried, 45mL tetrahydrofurans are added, weigh 0.3 g hexachlorocyclotriph,sphazenes and 0.3 g trimerizations
Cyanamide, 0.8 g triamylamines are added thereto after well mixed, immediately sealed flask, in ultrasonic cleaner under the conditions of 30 DEG C
（240 W, 80 kHz）Reacted 2 hours in water-bath.Reaction centrifuges after terminating, and washs centrifugation with ethanol and deionized water respectively
Product 4 times, finally product is dried in vacuo 10 hours under the conditions of 80 DEG C, obtains solid polyphosphazene microspheres.
Obtained solid polyphosphazene microspheres are placed in porcelain boat and delivered in retort, first leads to argon gas and drives away retort in 1 hour
In air, be then to slowly warm up to 550 DEG C with 15 DEG C/min heating rate, be incubated 2 hours, then proceed to be warming up to
700 DEG C, insulation is naturally cooling to room temperature after 10 hours, obtains being rich in mesoporous hollow carbon balls.
Embodiment 9
A kind of method that self-template prepares hollow carbon balls, step are as follows：
In the flask that 150 mL are dried, 50mL toluene is added, weighs 0.4 g hexachlorocyclotriph,sphazenes and 0.4 g 4,4 '-two
Hydroxy benzophenone alkane, 0.4 g sodium carbonate is added thereto after well mixed, immediately sealed flask, in ultrasound under the conditions of 30 DEG C
Ripple washer（240 W, 40 kHz）Reacted 3 hours in water-bath.Reaction centrifuges after terminating, and uses ethanol and deionized water respectively
Product, is finally dried in vacuo 10 hours, obtains solid polyphosphazene microspheres by washing centrifugation product 3 times under the conditions of 80 DEG C.
Obtained solid polyphosphazene microspheres are placed in porcelain boat and delivered in retort, first leads to argon gas and drives away retort in 1 hour
In air, be then to slowly warm up to 550 DEG C with 20 DEG C/min heating rate, be incubated 2 hours, then proceed to be warming up to
750 DEG C, insulation is naturally cooling to room temperature after 4 hours, obtains being rich in mesoporous hollow carbon balls.
Embodiment 10
A kind of method that self-template prepares hollow carbon balls, step are as follows：
In the flask that 150 mL are dried, add 55mL n-hexanes, weigh 0.12 g hexachlorocyclotriph,sphazenes and 0.5 g 4,4 '-
Dihydroxydiphenylsulisomer, 0.5 g potassium carbonate is added thereto after well mixed, immediately sealed flask, in ultrasound under the conditions of 30 DEG C
Ripple washer（220 W, 70 kHz）Reacted 3 hours in water-bath.Reaction centrifuges after terminating, and uses ethanol and deionized water respectively
Product, is finally dried in vacuo 18 hours, obtains solid polyphosphazene microspheres by washing centrifugation product 4 times under the conditions of 75 DEG C.
Obtained solid polyphosphazene microspheres are placed in porcelain boat and delivered in retort, first leads to argon gas and drives away retort in 1 hour
In air, be then to slowly warm up to 580 DEG C with 20 DEG C/min heating rate, be incubated 2 hours, then proceed to be warming up to
700 DEG C, insulation is naturally cooling to room temperature after 6 hours, obtains being rich in mesoporous hollow carbon balls.
Embodiment 11
A kind of method that self-template prepares hollow carbon balls, step are as follows：
In the flask that 150 mL are dried, add 60mL n-hexanes, weigh 0.5 g hexachlorocyclotriph,sphazenes and 0.6 g 4,4 '-
MDA, 1.4 g potassium carbonate are added thereto after well mixed, immediately sealed flask, in ultrasound under the conditions of 20 DEG C
Ripple washer（240 W, 70 kHz）Reacted 4 hours in water-bath.Reaction centrifuges after terminating, and uses ethanol and deionized water respectively
Product, is finally dried in vacuo 14 hours, obtains solid polyphosphazene microspheres by washing centrifugation product 4 times under the conditions of 75 DEG C.
Obtained solid polyphosphazene microspheres are placed in porcelain boat and delivered in retort, first leads to argon gas and drives away retort in 1 hour
In air, be then to slowly warm up to 590 DEG C with 18 DEG C/min heating rate, be incubated 2 hours, then proceed to be warming up to
740 DEG C, insulation is naturally cooling to room temperature after 8 hours, obtains being rich in mesoporous hollow carbon balls.
The foregoing is merely illustrative of the preferred embodiments of the present invention, is not intended to limit the invention, all essences in the present invention
God any modification, equivalent substitution and improvements made etc., should be included in the scope of the protection with principle.
Claims (9)
1. a kind of method that self-template prepares hollow carbon balls, it is characterised in that step is as follows：
（1）Hexachlorocyclotriph,sphazene and comonomer are scattered in organic solvent at room temperature；Then acid binding agent is added, in 20~30
The h of ultrasonic reaction 2~6, obtains reaction solution under the conditions of DEG C；
（2）By step（1）In reaction solution centrifuge, washed using ethanol and deionized water, be dried in vacuo after washing afterwards
Obtain solid polyphosphazene microspheres；
（3）By step（2）In obtained solid polyphosphazene microspheres be placed in retort, be passed through nitrogen or argon gas 1h, afterwards high temperature
Sintering obtains hollow carbon balls.
2. the method that self-template according to claim 1 prepares hollow carbon balls, it is characterised in that：The step（1）In six
The phosphonitrile of chlorine ring three, comonomer, the mass ratio of organic solvent and acid binding agent are（4-50）：（3-60）：（3000-6000）：（50-
140）.
3. the method that self-template according to claim 2 prepares hollow carbon balls, it is characterised in that：The step（1）In altogether
Polycondensation monomer be phloroglucin, hydroquinones, resorcinol, p-phenylenediamine, melamine, 4,4 '-dioxydiphenyl methane, 4,
In 4 '-dihydroxydiphenylsulisomer, 4,4' diaminodiphenyl sulfone, 4,4 '-MDA or 4,4 '-diaminodiphenyl ether
Any one.
4. the method that self-template according to claim 2 prepares hollow carbon balls, it is characterised in that：The step（1）In have
Solvent is at least one of ethanol, propyl alcohol, acetonitrile, acetone, tetrahydrofuran, toluene or n-hexane.
5. the method that self-template according to claim 2 prepares hollow carbon balls, it is characterised in that：The step（1）Tie up acid
Agent is any one in triethylamine, tripropyl amine (TPA), tri-n-butylamine, triamylamine, sodium carbonate or potassium carbonate.
6. the method that self-template according to claim 2 prepares hollow carbon balls, it is characterised in that：The step（1）In surpass
Acoustical power is 100~240 W, and supersonic frequency is 40-80 kHz.
7. the method that the self-template according to claim any one of 2-6 prepares hollow carbon balls, it is characterised in that：The step
（2）In vacuum drying temperature be 50-80 DEG C, drying time 10-24h.
8. the method that self-template according to claim 7 prepares hollow carbon balls, it is characterised in that：The step（3）In lead to
After entering nitrogen or argon gas 1h, 550-600 DEG C of insulation 0.5-2 h is warming up to 1~20 DEG C/min heating rate, afterwards with 1~
20 DEG C/min heating rate heats up 700~1000 DEG C, is incubated 2-10 h, naturally cools to room temperature and obtain hollow carbon balls.
9. the method that self-template according to claim 8 prepares hollow carbon balls, it is characterised in that：The step（3）It is hollow
The particle diameter of carbon ball is 450~560 nm.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711164047.1A CN107673323A (en) | 2017-11-21 | 2017-11-21 | A kind of method that self-template prepares hollow carbon balls |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711164047.1A CN107673323A (en) | 2017-11-21 | 2017-11-21 | A kind of method that self-template prepares hollow carbon balls |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN107673323A true CN107673323A (en) | 2018-02-09 |
Family
ID=61149891
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201711164047.1A Pending CN107673323A (en) | 2017-11-21 | 2017-11-21 | A kind of method that self-template prepares hollow carbon balls |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN107673323A (en) |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108479724A (en) * | 2018-01-30 | 2018-09-04 | 郑州大学 | A kind of preparation method with high magnetic responsiveness iron-iron oxide@polyphosphazene magnetic nano chains |
| CN109137144A (en) * | 2018-08-06 | 2019-01-04 | 浙江工业大学 | The preparation method of molybdenum disulfide composite hollow carbon nano-fiber materials |
| CN111040185A (en) * | 2019-12-25 | 2020-04-21 | 嘉兴学院 | Multifunctional composite flame retardant CMSs-HCCP-CS and preparation method and application thereof |
| CN111363154A (en) * | 2020-03-09 | 2020-07-03 | 南华大学上虞高等研究院有限公司 | Preparation method, application and decoloring method of polyphosphazene microspheres containing amino |
| CN113410479A (en) * | 2021-06-17 | 2021-09-17 | 济南大学 | Preparation method and application of transition metal monoatomic and nitrogen-phosphorus-doped carbon sphere |
| CN113540447A (en) * | 2021-06-29 | 2021-10-22 | 暨南大学 | Preparation and application of ultra-long cycle polyatomic doping hollow carbon electrode material |
| CN114425301A (en) * | 2020-10-29 | 2022-05-03 | 伊斯拓通用设备江苏有限公司 | Nitrogen-phosphorus co-doped carbon material for adsorbing heavy metal ions and preparation method thereof |
| CN115155554A (en) * | 2021-07-12 | 2022-10-11 | 中国科学院青岛生物能源与过程研究所 | Nano hollow mesoporous carbon sphere supported platinum nanoparticle catalyst and preparation method thereof |
| CN117504822B (en) * | 2023-11-30 | 2024-07-16 | 大连医科大学附属第二医院 | Metal-loaded nano carbon sphere and preparation method and application thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20110027376A1 (en) * | 2007-12-11 | 2011-02-03 | Nanyang Technological University | Hollow Multi-Layered Microspheres for Delivery of Hydrophilic Active Compounds |
| CN102583312A (en) * | 2012-02-09 | 2012-07-18 | 郑州大学 | Method for preparing porous carbon spheres doped with nitrogen and phosphorus and application |
| CN105523541A (en) * | 2016-01-29 | 2016-04-27 | 上海交通大学 | Heteroatom doped hollow porous carbon microspheres and preparation method thereof |
| CN105621390A (en) * | 2015-12-31 | 2016-06-01 | 上海交通大学 | Preparation method of heteroatom-doped carbon hollow microspheres |
| CN106185865A (en) * | 2016-07-19 | 2016-12-07 | 西安交通大学 | A kind of preparation method of hollow nano carbon microsphere |
-
2017
- 2017-11-21 CN CN201711164047.1A patent/CN107673323A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20110027376A1 (en) * | 2007-12-11 | 2011-02-03 | Nanyang Technological University | Hollow Multi-Layered Microspheres for Delivery of Hydrophilic Active Compounds |
| CN102583312A (en) * | 2012-02-09 | 2012-07-18 | 郑州大学 | Method for preparing porous carbon spheres doped with nitrogen and phosphorus and application |
| CN105621390A (en) * | 2015-12-31 | 2016-06-01 | 上海交通大学 | Preparation method of heteroatom-doped carbon hollow microspheres |
| CN105523541A (en) * | 2016-01-29 | 2016-04-27 | 上海交通大学 | Heteroatom doped hollow porous carbon microspheres and preparation method thereof |
| CN106185865A (en) * | 2016-07-19 | 2016-12-07 | 西安交通大学 | A kind of preparation method of hollow nano carbon microsphere |
Non-Patent Citations (2)
| Title |
|---|
| TINGJUN PAN ET AL: ""Controlled Fabrication of Uniform Hollow Bowl-Shaped Microspheres Based on Polyphosphazene Material"", 《MACROMOL. CHEM. PHYS. 》 * |
| 潘亭军: ""多形功能性聚膦腈微纳米材料的可控制备"", 《中国优秀硕士学位论文全文数据库（电子期刊）工程科技Ⅰ辑》 * |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108479724A (en) * | 2018-01-30 | 2018-09-04 | 郑州大学 | A kind of preparation method with high magnetic responsiveness iron-iron oxide@polyphosphazene magnetic nano chains |
| CN109137144A (en) * | 2018-08-06 | 2019-01-04 | 浙江工业大学 | The preparation method of molybdenum disulfide composite hollow carbon nano-fiber materials |
| CN111040185A (en) * | 2019-12-25 | 2020-04-21 | 嘉兴学院 | Multifunctional composite flame retardant CMSs-HCCP-CS and preparation method and application thereof |
| CN111363154A (en) * | 2020-03-09 | 2020-07-03 | 南华大学上虞高等研究院有限公司 | Preparation method, application and decoloring method of polyphosphazene microspheres containing amino |
| CN114425301A (en) * | 2020-10-29 | 2022-05-03 | 伊斯拓通用设备江苏有限公司 | Nitrogen-phosphorus co-doped carbon material for adsorbing heavy metal ions and preparation method thereof |
| CN113410479A (en) * | 2021-06-17 | 2021-09-17 | 济南大学 | Preparation method and application of transition metal monoatomic and nitrogen-phosphorus-doped carbon sphere |
| CN113540447A (en) * | 2021-06-29 | 2021-10-22 | 暨南大学 | Preparation and application of ultra-long cycle polyatomic doping hollow carbon electrode material |
| CN115155554A (en) * | 2021-07-12 | 2022-10-11 | 中国科学院青岛生物能源与过程研究所 | Nano hollow mesoporous carbon sphere supported platinum nanoparticle catalyst and preparation method thereof |
| CN115155554B (en) * | 2021-07-12 | 2024-04-26 | 中国科学院青岛生物能源与过程研究所 | Nanometer hollow mesoporous carbon sphere supported platinum nanoparticle catalyst and preparation method thereof |
| CN117504822B (en) * | 2023-11-30 | 2024-07-16 | 大连医科大学附属第二医院 | Metal-loaded nano carbon sphere and preparation method and application thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN107673323A (en) | A kind of method that self-template prepares hollow carbon balls | |
| CN104709906B (en) | Preparation method of three dimensional graded porous activated carbon material | |
| Lu et al. | Synthesis of discrete and dispersible hollow carbon nanospheres with high uniformity by using confined nanospace pyrolysis | |
| CN101618869B (en) | Method for preparing small-size meso-porous hollow carbon sphere | |
| CN106207108B (en) | Si-C composite material and the preparation method and application thereof based on macromolecule foaming microballoon | |
| CN110508222A (en) | Monodisperse core-shell particles and preparation method thereof with mesoporous silicon oxide shell | |
| CN101759178B (en) | Preparation method for hollow carbon hemisphere | |
| CN105523541A (en) | Heteroatom doped hollow porous carbon microspheres and preparation method thereof | |
| TWI757680B (en) | A kind of composite microsphere with radial fibrous mesoporous shell layer/hollow core layer structure and preparation method thereof | |
| CN105502342A (en) | Method for preparing nanometer hollow carbon spheres with dopamine serving as carbon source | |
| CN104671233B (en) | A kind of preparation method of foamy graphite alkene | |
| CN112225204B (en) | Control method and equipment for graphene orientation in graphene sponge | |
| CN107863507B (en) | The method that Suspended Emulsion Polymerization method prepares silicon-carbon cathode material | |
| CN103545077B (en) | The Fe that oxazine ring is modified 3o 4siO 2magnetic Nano microsphere and preparation method thereof and application | |
| CN106083046A (en) | A kind of preparation method of Graphene/polyimides copolymerization heat conducting film | |
| CN108640102B (en) | Preparation method and application of hollow carbon sphere micro-nano aggregate/sulfur composite material | |
| CN105883805B (en) | A kind of preparation method of the high-specific surface area carbosphere based on tea seed shell base | |
| CN106450208B (en) | A kind of silicon composite and preparation method thereof for cathode of lithium battery | |
| CN107790105A (en) | A kind of preparation method of ammonification elasticity silicon substrate composite aerogel | |
| Zhou et al. | Scalable preparation of hollow polymer and carbon microspheres by spray drying and their application in low-density syntactic foam | |
| CN110482521A (en) | A kind of preparation method of hollow carbon balls | |
| CN110452480B (en) | Preparation method of ultra-light heat-insulating flexible aerogel | |
| CN110092368A (en) | A kind of double-layer structure phenolic aldehyde hard carbon microballoon and its preparation method and application | |
| CN106145127A (en) | A kind of preparation method of hollow microsphere silicon dioxide | |
| CN110342509B (en) | Method for preparing hydroxyl nano-diamond by using efficient reducing agent red aluminum and hydroxyl nano-diamond prepared by method |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| CB02 | Change of applicant information | ||
| CB02 | Change of applicant information |
Address after: 451191 No. 1 Huaihe Road, Shuang Hu Economic and Technological Development Zone, Xinzheng, Zhengzhou, Henan Applicant after: Zhongyuan University of Technology Address before: 451191 No. 1 Huaihe Road, Shuanghu Town Economic and Technological Development Zone, Zhengzhou City, Henan Province Applicant before: Zhongyuan University of Technology |
|
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20180209 |