CN109081327A - A kind of bowl-shape porous carbon microsphere and preparation method thereof - Google Patents
A kind of bowl-shape porous carbon microsphere and preparation method thereof Download PDFInfo
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- CN109081327A CN109081327A CN201811239112.7A CN201811239112A CN109081327A CN 109081327 A CN109081327 A CN 109081327A CN 201811239112 A CN201811239112 A CN 201811239112A CN 109081327 A CN109081327 A CN 109081327A
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- 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
- C01B32/05—Preparation or purification of carbon not covered by groups C01B32/15, C01B32/20, C01B32/25, C01B32/30
Abstract
The invention belongs to field of new materials, in particular to a kind of bowl-shape porous carbon microsphere and preparation method thereof.Using monodisperse cross-linked soft core/hard shell polystyrene microsphere as template, bowl-shape porous carbon microsphere has successively been prepared in the heat treatment in the hydrolysis of Surfaces of Polystyrene Microparticles, air, the carbonization treatment under nitrogen atmosphere and hf etching by ethyl orthosilicate.This method simple process, the bowl-shape carbosphere of preparation have many advantages, such as size uniformity, good dispersion, surface have it is big lead directly to it is mesoporous.
Description
Technical field
The invention belongs to field of new materials, in particular to a kind of bowl-shape porous carbon microsphere and preparation method thereof.
Background technique
In recent years, since bowl-shape microballoon has hollow, recess, opening and aspherical weak symmetrical structure, make it in light
, medicament slow release, catalysis, supercapacitor, controlled release, lithium ion battery, molecule printing etc. have shown good
Application prospect.
The most common method for preparing bowl-shape microballoon has colloid monolayer crystal template method, bowl-type array film template, lures
Lead growth method, hydridization/special-shaped particle method, seeded polymerization and hollow microsphere invagination method, wherein hollow microsphere invagination method wrap again
Include solvent treatment method and heat treating process.
It uses polystyrene (PS) microballoon of soft core/hard shell for construction unit, passes through solvent treatment method, document [Journal
Of Colloid and Interface Science 2011,358,437-443] it is prepared for bowl-shape polymer microballoon, and
Document [Physical Chemistry Chemical Physics, 2013,15,17786-17792; RSC Advances
2016,6,16141-16149] then it is prepared for bowl-shape carbosphere.Using heat-treating methods, document [Colloid and
Polymer Science 2017,295,2151-2161] it is prepared for ordered arrangement and dispersible bowl-shape polymer is micro-
Ball.Meanwhile domestic applications number provide a kind of preparation side of monodisperse carbon nano bowl for 201310006528.5 patent of invention
Method.Domestic applications number provide a kind of titanium dioxide bowl particle for 201110200005.5 patent of invention or dumb-bell shape is hollow
Particle and preparation method thereof.Although these reports enrich the preparation method of bowl-shape microballoon, the application neck of these microballoons has been expanded
Domain, but due to there was only the micropore of random distribution or lesser mesoporous in these bowl-shape microballoon ball walls, this not only makes biological big point
Son can not also be significantly greatly increased ion and other materials in the transport resistance of ball wall, limit answering for these microballoons by ball wall
With.And there is the big mesoporous bowl-shape microballoon that leads directly to still not report up to now on surface.Therefore, developing a kind of surface has
The larger preparation method for leading directly to mesoporous bowl-shape carbosphere theoretical and application value with higher.
Summary of the invention
To solve the above-mentioned problems, the present invention provides a kind of bowl-shape porous carbon microsphere and preparation method thereof.This method preparation
Bowl-shape porous carbon microsphere there is big straight-through Jie with of uniform size, good dispersion, without organic reagent etching and surface
The advantages that hole.
A kind of bowl-shape porous carbon microsphere and preparation method thereof, which is characterized in that the complex microsphere has the shape of bowl-like,
Bowl wall is made of two layers of carbon film structure, have in bowl wall it is big lead directly to it is mesoporous.
The size of the bowl-shape porous carbon microsphere is between 200-500nm.
The bowl-shape porous carbon microsphere bowl wall is with a thickness of 15-35nm.
Having diameter on the bowl-shape porous carbon microsphere wall is that leading directly to for 10-40nm is mesoporous.
A kind of bowl-shape porous carbon microsphere and preparation method thereof, specific preparation process are as follows:
1) soft core/hard shell polystyrene microsphere preparation: a certain amount of styrene is measured, is added dropwise in 90mL deionized water
In, it is passed through high pure nitrogen stirring 30min, 70 DEG C is heated to, the deionized water solution of 10mL potassium peroxydisulfate containing 0.12g is then added
As initiator, 3h is stirred at 70 DEG C, then in above-mentioned system with being added a certain amount of divinylbenzene the reaction was continued for 24 hours,
It can be obtained soft core/hard shell polystyrene microsphere that diameter is 250-600nm.
2) polystyrene/SiO2The preparation of complex microsphere: the polystyrene microsphere ultrasound prepared in a certain amount of step 1) is taken
It is scattered in 160mL ethyl alcohol, being subsequently added into a certain amount of ethyl orthosilicate and ammonium hydroxide magnetic stirrer 12h makes positive silicic acid
Ethyl ester hydrolyzes and is self-assembled to microsphere surface, can be obtained polystyrene/SiO2Complex microsphere.
3) bowl-shape polystyrene/SiO2The preparation of complex microsphere: all polystyrene/SiO that will be prepared in step 22It is multiple
Conjunction microballoon is heated to 270-400 DEG C with Muffle furnace with the heating rate of 5 DEG C/min and keeps the temperature 2h again, and bowl-shape polyphenyl second can be obtained
Alkene/SiO2Complex microsphere.
4) bowl-shape C/SiO2The preparation of complex microsphere: all bowl-shape polystyrene/SiO that will be prepared in step 3)2It is compound micro-
Ball is heated to 700 DEG C in nitrogen atmosphere with the heating rate of 2 DEG C/min and keeps the temperature 2h, bowl-shape C/SiO can be obtained2It is compound
Microballoon.
5) preparation of bowl-shape porous carbon microsphere: all bowl-shape C/SiO that will be prepared in step 4)2Complex microsphere 20mL matter
The HF solution etches 2h that concentration is 10wt% is measured, bowl-shape porous carbon microsphere can be obtained.
A kind of bowl-shape porous carbon microsphere provided by the present invention and preparation method thereof, the carbosphere phase with current report
Than having the advantage that
1) without removing template microsphere using organic solvent during prepared by microballoon, preparation process is simple and environmentally-friendly；
2) the bowl-shape porous carbon microsphere prepared is of uniform size, good dispersion；
3) it is that leading directly to for 10-40nm is mesoporous that bowl-shape microsphere surface, which has diameter, is conducive to transmission of the substance inside and outside microballoon.
Detailed description of the invention
Fig. 1 is the electron scanning micrograph for the bowl-shape porous carbon microsphere that the embodiment of the present invention 1 obtains.
Fig. 2 is the transmission electron microscope photo for the bowl-shape porous carbon microsphere that the embodiment of the present invention 1 obtains.
Specific embodiment
Principles and features of the present invention are described with reference to embodiments, listed give an actual example is served only for explaining this hair
It is bright, not limit the scope of the invention.
Embodiment 1:
1) soft core/hard shell polystyrene microsphere preparation: measuring 5.28mL styrene, be added dropwise in 90mL deionized water,
It is passed through high pure nitrogen stirring 30min, is heated to 70 DEG C, the deionized water solution that 10mL potassium peroxydisulfate containing 0.12g is then added is made
For initiator, 3h is stirred at 70 DEG C, then above-mentioned system be added 1.32mL divinylbenzene the reaction was continued for 24 hours, can obtain
To soft core/hard shell polystyrene microsphere.
2) polystyrene/SiO2The preparation of complex microsphere: rapid 1) the middle polystyrene microsphere ultrasonic disperse prepared of 0.6g is taken
In 160mL ethyl alcohol, being subsequently added into 3.6mL ammonium hydroxide and 1.65mL ethyl orthosilicate magnetic stirrer 12h makes positive silicic acid
Ethyl ester hydrolyzes and is self-assembled to microsphere surface, can be obtained polystyrene/SiO2Complex microsphere.
3) bowl-shape polystyrene/SiO2The preparation of complex microsphere: all polystyrene/SiO that will be prepared in step 22It is multiple
It closes microballoon to be heated to 350 DEG C in Muffle furnace with the heating rate of 5 DEG C/min and keep the temperature 2h, bowl-shape polyphenyl second can be obtained
Alkene/SiO2Complex microsphere.
4) bowl-shape C/SiO2The preparation of complex microsphere: all bowl-shape polystyrene/SiO that will be prepared in step 3)2It is compound micro-
Ball is heated to 700 DEG C in nitrogen atmosphere with the heating rate of 2 DEG C/min and keeps the temperature 2h, and bowl-shape C/SiO can be obtained2It is compound micro-
Ball.
5) preparation of bowl-shape porous carbon microsphere: all bowl-shape C/SiO that will be prepared in step 4)2Complex microsphere 20mL matter
The HF solution etches 2h that concentration is 10wt% is measured, bowl-shape porous carbon microsphere can be obtained.
Embodiment 2:
1) it soft core/hard shell polystyrene microsphere preparation: is carried out according to embodiment 1.
2) polystyrene/SiO2The preparation of complex microsphere: it is carried out according to embodiment 1.
3) bowl-shape polystyrene/SiO2The preparation of complex microsphere: all polystyrene/SiO that will be prepared in step 22It is multiple
It closes microballoon to be heated to 370 DEG C in Muffle furnace with the heating rate of 5 DEG C/min and keep the temperature 2h, bowl-shape polyphenyl second can be obtained
Alkene/SiO2Complex microsphere.
4) bowl-shape C/SiO2The preparation of complex microsphere: it is carried out according to embodiment 1.
5) it the preparation of bowl-shape porous carbon microsphere: is carried out according to embodiment 1.
Embodiment 3:
1) it soft core/hard shell polystyrene microsphere preparation: is carried out according to embodiment 1.
2) polystyrene/SiO2The preparation of complex microsphere: it is carried out according to embodiment 1.
3) bowl-shape polystyrene/SiO2The preparation of complex microsphere: all polystyrene/SiO that will be prepared in step 22It is multiple
It closes microballoon to be heated to 400 DEG C in Muffle furnace with the heating rate of 5 DEG C/min and keep the temperature 2h, bowl-shape polyphenyl second can be obtained
Alkene/SiO2Complex microsphere.
4) bowl-shape C/SiO2The preparation of complex microsphere: it is carried out according to embodiment 1.
5) it the preparation of bowl-shape porous carbon microsphere: is carried out according to embodiment 1.
Embodiment 4:
1) soft core/hard shell polystyrene microsphere preparation: measuring 5.28mL styrene, be added dropwise in 90mL deionized water,
It is passed through high pure nitrogen stirring 30min, is heated to 70 DEG C, the deionized water solution that 10mL potassium peroxydisulfate containing 0.12g is then added is made
For initiator, 3h is stirred at 70 DEG C, then above-mentioned system be added 1.76mL divinylbenzene the reaction was continued for 24 hours, can obtain
To soft core/hard shell polystyrene microsphere.
2) polystyrene/SiO2The preparation of complex microsphere: it is carried out according to embodiment 1.
3) bowl-shape polystyrene/SiO2The preparation of complex microsphere: it is carried out according to embodiment 1.
4) bowl-shape C/SiO2The preparation of complex microsphere: it is carried out according to embodiment 1.
5) it the preparation of bowl-shape porous carbon microsphere: is carried out according to embodiment 1.
Embodiment 5:
1) soft core/hard shell polystyrene microsphere preparation: measuring 5.28mL styrene, be added dropwise in 90mL deionized water,
It is passed through high pure nitrogen stirring 30min, is heated to 70 DEG C, the deionized water solution that 10mL potassium peroxydisulfate containing 0.12g is then added is made
For initiator, 3h is stirred at 70 DEG C, then above-mentioned system be added 2.26mL divinylbenzene the reaction was continued for 24 hours, can obtain
To soft core/hard shell polystyrene microsphere.
2) polystyrene/SiO2The preparation of complex microsphere: it is carried out according to embodiment 1.
3) bowl-shape polystyrene/SiO2The preparation of complex microsphere: it is carried out according to embodiment 1.
4) bowl-shape C/SiO2The preparation of complex microsphere: it is carried out according to embodiment 1.
5) it the preparation of bowl-shape porous carbon microsphere: is carried out according to embodiment 1.
Embodiment 6:
1) it soft core/hard shell polystyrene microsphere preparation: is carried out according to embodiment 1.
2) polystyrene/SiO2The preparation of complex microsphere: the polystyrene microsphere ultrasound prepared in 0.6g step 1) point is taken
It dissipates in 160mL ethyl alcohol, being subsequently added into 2.4mL ammonium hydroxide and 1.65mL ethyl orthosilicate magnetic stirrer 12h makes positive silicon
Hydrolysis of ethyl acetate is simultaneously self-assembled to microsphere surface, can be obtained polystyrene/SiO2Complex microsphere.
3) bowl-shape polystyrene/SiO2The preparation of complex microsphere: it is carried out according to embodiment 1.
4) bowl-shape C/SiO2The preparation of complex microsphere: it is carried out according to embodiment 1.
5) it the preparation of bowl-shape porous carbon microsphere: is carried out according to embodiment 1.
Embodiment 7:
1) it soft core/hard shell polystyrene microsphere preparation: is carried out according to embodiment 1.
2) polystyrene/SiO2The preparation of complex microsphere: polystyrene/SiO2The preparation of complex microsphere: 0.6g step 1) is taken
The polystyrene microsphere ultrasonic disperse of middle preparation is subsequently added into 4.8mL ammonium hydroxide and 1.65mL ethyl orthosilicate in 160mL ethyl alcohol
Make teos hydrolysis with magnetic stirrer 12h and be self-assembled to microsphere surface, can be obtained polystyrene/SiO2It is multiple
Close microballoon.
3) bowl-shape polystyrene/SiO2The preparation of complex microsphere: it is carried out according to embodiment 1.
4) bowl-shape C/SiO2The preparation of complex microsphere: it is carried out according to embodiment 1.
5) it the preparation of bowl-shape porous carbon microsphere: is carried out according to embodiment 1.
The structural parameters of each obtained bowl-shape porous carbon microsphere of embodiment are as shown in table 1.
Examples detailed above shows: when preparing bowl-shape porous carbon microsphere using each embodiment, improving bowl-shape polystyrene/SiO2
The temperature (embodiment 1,2,3) being heat-treated in the preparation step of complex microsphere can in the diameter for reducing bowl-shape porous carbon microsphere and
Increase the size of microsphere surface clear opening while wall thickness；Increase used in soft core/hard shell polystyrene microsphere preparation step
Crosslinking agent dosage (embodiment 1,4,5) can then be reduced while increasing the diameter and wall thickness of bowl-shape porous carbon microsphere it is micro-
The size of ball surface clear opening；Increase polystyrene/SiO2The dosage of ammonium hydroxide used in the preparation step of complex microsphere (is implemented
Example 1,6,7) can then increase microsphere surface clear opening in the case where not changing the diameter and wall thickness of bowl-shape porous carbon microsphere
Size.
The above embodiments merely illustrate the technical concept and features of the present invention, and its object is to allow person skilled in the art
Scholar cans understand the content of the present invention and implement it accordingly, and it is not intended to limit the scope of the present invention.It is all according to the present invention
Equivalent change or modification made by Spirit Essence, should be covered by the protection scope of the present invention.
Claims (5)
1. a kind of bowl-shape porous carbon microsphere and preparation method thereof, which is characterized in that the complex microsphere has the shape of bowl-like, bowl
Wall is made of two layers of carbon film structure, have in bowl wall it is big lead directly to it is mesoporous.
2. bowl-shape porous carbon microsphere according to claim 1 and preparation method thereof, which is characterized in that the ruler of bowl-shape carbosphere
It is very little between 200-500nm.
3. bowl-shape porous carbon microsphere according to claim 1 and preparation method thereof, which is characterized in that the wall thickness of bowl-shape microballoon
For 15-35nm.
4. bowl-shape porous carbon microsphere according to claim 1 and preparation method thereof, which is characterized in that on the wall of bowl-shape microballoon
Having diameter is that leading directly to for 10-40nm is mesoporous.
5. bowl-shape porous carbon microsphere and preparation method thereof described in one of -4, preparation process include following according to claim 1
Step: 1. soft core/hard shell polystyrene microsphere preparation: a certain amount of styrene is measured, is added dropwise in 90mL deionized water
In, it is passed through high pure nitrogen stirring 30min, 70 DEG C is heated to, the deionized water solution of 10mL potassium peroxydisulfate containing 0.12g is then added
As initiator, 3h is stirred at 70 DEG C, is then added a certain amount of divinylbenzene in the above system the reaction was continued for 24 hours,
It can be obtained soft core/hard shell polystyrene microsphere that diameter is 250-600nm；2. polystyrene/SiO2The preparation of complex microsphere:
Taking a certain amount of step, 1. the middle polystyrene microsphere ultrasonic disperse prepared is subsequently added into a certain amount of positive silicon in 160mL ethyl alcohol
Acetoacetic ester and ammonium hydroxide magnetic stirrer 12h make teos hydrolysis and are self-assembled to microsphere surface, can be obtained poly-
Styrene/SiO2Complex microsphere；3. bowl-shape polystyrene/SiO2The preparation of complex microsphere: by step 2. in prepare all polyphenyl
Ethylene/SiO2Complex microsphere is heated to 270-400 DEG C with Muffle furnace with the heating rate of 5 DEG C/min and keeps the temperature 2h again, can be obtained
Bowl-shape polystyrene/SiO2Complex microsphere；4. bowl-shape C/SiO2The preparation of complex microsphere: by step 3. in prepare all bowls
Shape polystyrene/SiO2Complex microsphere is heated to 700 DEG C in nitrogen atmosphere with the heating rate of 2 DEG C/min and keeps the temperature 2h, i.e.,
Bowl-shape C/SiO can be obtained2Complex microsphere；5. the preparation of bowl-shape porous carbon microsphere: by step 4. in prepare all bowl-shape C/SiO2
The HF solution etches 2h that complex microsphere is 10wt% with 20mL mass concentration, can be obtained bowl-shape porous carbon microsphere.
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Cited By (4)
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| CN110171812A (en) * | 2019-05-27 | 2019-08-27 | 北京科技大学 | Multi-layer porous hollow bowl-type carbon material of one kind and preparation method thereof |
| CN113745010A (en) * | 2021-08-11 | 2021-12-03 | 上海交通大学 | Ternary composite material and preparation method and application thereof |
| CN113845108A (en) * | 2021-10-29 | 2021-12-28 | 郑州大学 | Hollow carbon bowl with adjustable shell layer distance and shell thickness and preparation method thereof |
| CN114735696A (en) * | 2022-06-09 | 2022-07-12 | 国家电投集团氢能科技发展有限公司 | Hollow bowl-shaped carbon carrier and preparation method thereof, platinum-based catalyst and membrane electrode |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110171812A (en) * | 2019-05-27 | 2019-08-27 | 北京科技大学 | Multi-layer porous hollow bowl-type carbon material of one kind and preparation method thereof |
| CN113745010A (en) * | 2021-08-11 | 2021-12-03 | 上海交通大学 | Ternary composite material and preparation method and application thereof |
| CN113845108A (en) * | 2021-10-29 | 2021-12-28 | 郑州大学 | Hollow carbon bowl with adjustable shell layer distance and shell thickness and preparation method thereof |
| CN114735696A (en) * | 2022-06-09 | 2022-07-12 | 国家电投集团氢能科技发展有限公司 | Hollow bowl-shaped carbon carrier and preparation method thereof, platinum-based catalyst and membrane electrode |
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Application publication date: 20181225 |