CN109354007A - A kind of regulatable bivalve layer hollow caged carbosphere of foreign components of structure - Google Patents
A kind of regulatable bivalve layer hollow caged carbosphere of foreign components of structure Download PDFInfo
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- CN109354007A CN109354007A CN201811326041.4A CN201811326041A CN109354007A CN 109354007 A CN109354007 A CN 109354007A CN 201811326041 A CN201811326041 A CN 201811326041A CN 109354007 A CN109354007 A CN 109354007A
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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
- C01B32/15—Nano-sized carbon materials
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
- B01J13/02—Making microcapsules or microballoons
- B01J13/06—Making microcapsules or microballoons by phase separation
- B01J13/14—Polymerisation; cross-linking
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
Abstract
The invention belongs to field of new materials, in particular to a kind of regulatable bivalve layer hollow caged carbosphere of foreign components of structure.Using soft core/hard shell polystyrene microsphere of crosslinking as template, successively by ethyl orthosilicate in the hydrolysis of microsphere surface, dopamine in processes such as the polymerization of microsphere surface, carbonization treatment and hf etchings, be prepared for the bivalve layer hollow caged carbosphere of foreign components.The hollow caged carbosphere of this method preparation has many advantages, such as that of uniform size, good dispersion, inside and outside carbon shell component difference, inside and outside carbon shell layer surface have straight-through large scale mesoporous or macropore, simultaneously, the cavity size of hollow caged carbosphere, the thickness of each carbon shell and straight-through large scale is mesoporous or the diameter of macropore can be achieved to adjust, are the innovations of hollow carbon method for preparing microsphere.
Description
Technical field
The invention belongs to field of new materials, in particular to a kind of regulatable bivalve layer hollow caged carbon of foreign components of structure is micro-
Ball.
Background technique
In order to meet the growing energy demand of people, the energy system for developing high energy conversion and storage efficiency becomes
Must be more more and more urgent, and the exploitation of these systems is largely dependent upon the nano material with unique texture and function
Design and synthesis.In various energy storage devices, supercapacitor is because having ultrafast charge-discharge velocity, long recycling
Service life and excellent cyclical stability and receive the favor of people.The performance of supercapacitor is mainly determined by electrode material
It is fixed.Currently, including the electrode material that activated carbon, carbon fiber, graphene and carbon nanotube etc. have all been used as supercapacitor.So
And since these material surfaces only have small micropore, it is excessive to will lead to resistance to mass tranfer in charge and discharge process, causes high charge-discharge
The sharply decline of super capacitor specific capacity, affects the performance of supercapacitor under multiplying power.In addition, the carbon material of Heteroatom doping
The specific capacity that supercapacitor can be improved increases the polarity of carbon material surface and is conducive to the transmission and transfer of electronics and proton.
Hollow carbosphere with big hollow cavity, porous shell structurre and controllable surface nature due to urging
The fields such as change, absorption, biological medicine and energy storage have shown tempting application prospect.Domestic applications number are
The patent of invention of 200610114339.X provides a kind of preparation method of the hollow carbon micron-spheres of structured size, domestic applications number
A kind of preparation method of hollow carbon balls is provided for 200810113771.6 patent of invention, domestic applications number are
200910237792.3 patent of invention provide a kind of amphipathic Porous hollow carbosphere and the preparation method and application thereof, it is domestic
Application No. is 201110056936.2 patents of invention to provide a kind of preparation method of hyper-energy active electrical carbon hollow micro ball, domestic
A kind of preparation of N doping hollow carbon balls is provided application No. is 201210475554.8 patent of invention and is fired in direct methanol
Expect cell cathode in application, domestic applications number for 201410272106.7 patent of invention provide a kind of starch base it is porous in
Empty carbosphere and preparation method thereof, for 201410594717.3 patent of invention, to provide a kind of boron doping hollow for domestic applications number
The preparation of carbon ball and the application in cathode in direct methanol fuel cells, however on the hollow carbosphere ball wall of these methods preparation
Usually only micropore or lesser mesoporous can not solve the problems, such as that resistance to mass tranfer is excessive in supercapacitor use process.
In addition to this, it is compared with the electrode of super capacitor of the hollow carbosphere preparation by more shells, monoshell layer hollow carbon
The specific capacity of the device of microballoon preparation is lower, and resistance to mass tranfer is larger.This is because multilayer carbosphere has more active sites
With shorter ion transmission range.Although domestic applications number provide a kind of multilayer carbon for 201410588081.1 patent of invention
The preparation method of hollow sphere negative electrode material, document [Carbon 2015,86,235-244] is with hollow SnO2For template, preparation
The hollow carbosphere of bivalve layer of Heteroatom doping, document [Carbon 2016,99,514-522] is with the C/SiO of bivalve layer2For
Template is prepared for Fe3O4The bivalve layer carbosphere of doping, but not have straight-through large scale mesoporous for the shell of these microballoons
Or macropore, it is straight on the cavity size to the hollow carbosphere of bivalve layer, each layer wall thickness, carbon-coating component and carbon shell it is even more impossible to realize
Logical large scale is mesoporous or the aperture adjustment of macropore, this causes great obstruction to high performance supercapacitor is prepared.
Summary of the invention
To solve the above-mentioned problems, it is micro- to provide a kind of regulatable bivalve layer hollow caged carbon of foreign components of structure by the present invention
Ball.For this method using the crosslinked polystyrene microsphere of soft core/hard shell as template, the soft core part of the polystyrene microsphere is linear gathers
Styrene, hard shell part is the polystyrene of divinyl benzene crosslinked, then by ethyl orthosilicate in polystyrene microsphere table
Raspberry shape polystyrene/silica dioxide complex microsphere is constructed in the hydrolysis in face.Then by dopamine in raspberry shape polystyrene/bis-
The polymerization on silica complex microsphere surface has obtained polystyrene/silica dioxide/poly-dopamine complex microsphere of sandwich type.
Polyphenyl second linear in the crosslinked polystyrene microsphere of soft core/hard shell is then made by high temperature cabonization processing in a nitrogen atmosphere
The soft nuclear decomposition of alkene forms hollow cavity, and the polystyrene hard shell of crosslinking is carbonized to form internal layer carbon shell, and poly-dopamine is carbonized to be formed outside
Layer carbon shell, intermediate silica dioxide granule are embedded in the process and pierce through inside and outside carbon-coating, obtain hollow sandwich type C/SiO2/
C hybrid microspheres.Above-mentioned hybrid microspheres hf etching is finally removed into SiO2Nano particle, formation surface, which has, leads directly to big ruler
Very little mesoporous or macropore the bivalve layer hollow caged carbosphere of foreign components.
A kind of regulatable bivalve layer hollow caged carbosphere of foreign components of structure, which is characterized in that the microballoon center has
Hollow cavity, ball wall are made of inside and outside two layers of carbon shell, and the ingredient of internal layer carbon shell is common carbon material, and the ingredient of outer layer carbon shell is nitrogen
The carbon material of doping has straight-through large scale mesoporous or macropore on two layers of carbon shell, the cavity size of hollow caged carbosphere, inside and outside
Straight-through large scale on shell thickness and two layers of carbon shell is mesoporous or the diameter of macropore is adjustable.
The size of the hollow cavity of the microballoon can be adjusted between 210-550nm.
The thickness of the internal layer carbon shell of the microballoon can be adjusted between 10-30nm.
Straight-through large scale on the ectonexine carbon shell of the microballoon is mesoporous or the diameter of macropore can carry out between 35-90nm
It adjusts.
The outer layer carbon thickness of the shell of the microballoon can be adjusted between 35-110nm.
A kind of regulatable bivalve layer hollow caged carbosphere of foreign components of structure, preparation process include the following steps:
1) soft core/hard shell polystyrene (PS) microballoon preparation: measuring a certain amount of styrene, be added dropwise 120mL go from
In sub- water, it is passed through high pure nitrogen stirring 30min, 70 DEG C is heated to, it is water-soluble that a certain amount of deionization containing potassium peroxydisulfate is then added
Liquid stirs 4h as initiator at 70 DEG C, and a certain amount of cross-linker divinylbenzene and anti-is then added in the above system
Soft core/hard shell polystyrene microsphere that diameter is 250-600nm should be can be obtained for 24 hours.
2) raspberry shape PS/ silica (SiO2) complex microsphere preparation: take the PS microballoon prepared in a certain amount of step 1)
A certain amount of ethyl orthosilicate is then added into above-mentioned solution and stirs 30min, so in a certain amount of ethyl alcohol for ultrasonic disperse
A certain amount of ammonium hydroxide is added dropwise again afterwards and continues that raspberry shape PS/SiO can be obtained after stirring 10h2Complex microsphere.
3) sandwich type PS/SiO2The preparation of/poly-dopamine (PDA) complex microsphere: it takes and is prepared in a certain amount of step 2
The PS/SiO of raspberry shape2Complex microsphere ultrasonic disperse is ethyl alcohol: water=7: 1 in the mixed solvent in a certain amount of volume ratio, is added one
Trihydroxy aminomethane and dopamine are quantified, is mixed for 24 hours under room temperature, dopamine is in PS/SiO2Microsphere surface polymerization
Obtain the PS/SiO of sandwich type2/ PDA organic/inorganic complex microsphere.
4) hollow sandwich type C/SiO2The preparation of/C hybrid microspheres: it with the heating rate of 2 DEG C/min, will be made in step 3)
Standby all sandwich type polystyrene/silica dioxide/poly-dopamine complex microspheres are heated to 800 DEG C and are protected in nitrogen atmosphere
Hollow sandwich type C/SiO can be obtained in warm 2h2/ C hybrid microspheres.
5) preparation of the bivalve layer hollow caged carbosphere of foreign components: all hollow sandwich type C/ that will be prepared in step 4)
SiO2The HF that/C hybrid microspheres are 10wt% with 100mL concentration etches 2h and after centrifuge washing is handled, and it is different that bivalve layer can be obtained
The hollow caged carbosphere of component.
The regulatable bivalve layer hollow caged carbosphere of foreign components of a kind of structure provided by the present invention, with current report
Hollow carbon hybrid microspheres compared to having the advantage that
1) the caged carbosphere prepared is of uniform size, good dispersion；
2) ingredient of two layers of carbon shell is different inside and outside the caged carbosphere prepared, and internal layer carbon shell is common carbon film, and outer layer carbon shell is
The carbon film of N doping；
3) big ruler is led directly on the hollow cavity size of caged carbosphere, the thickness of inside and outside carbon shell and the inside and outside carbon shell prepared
Very little mesoporous or macropore diameter is adjustable.
Detailed description of the invention
Fig. 1 is that the scanning electron microscope for the bivalve layer hollow caged carbosphere of foreign components that the embodiment of the present invention 1 obtains is shone
Piece.
Fig. 2 is that the transmission electron microscope for the bivalve layer hollow caged carbosphere of foreign components that the embodiment of the present invention 1 obtains shines
Piece.
Fig. 3 is the high-amplification-factor transmission electricity for the bivalve layer hollow caged carbosphere of foreign components that the embodiment of the present invention 1 obtains
Sub- microscope photo.
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 PS microballoon preparation: 8mL styrene is measured, is added dropwise in 120mL deionized water, is passed through high-purity
Nitrogen gas stirring 30min is heated to 70 DEG C, the deionized water solution of 14mL potassium peroxydisulfate containing 0.16g is then added as initiator,
4h is stirred at 70 DEG C, then in the above system be added 1.8mL divinylbenzene the reaction was continued for 24 hours, can be obtained diameter is
The soft core of 250nm/hard shell PS microballoon.
2) raspberry shape PS/SiO2The preparation of complex microsphere: take the PS microballoon ultrasonic disperse that is prepared in 0.5g step 1) in
In 160mL ethyl alcohol, 1mL ethyl orthosilicate is then added into above-mentioned solution and stirs 30min, 20mL ammonium hydroxide is then added dropwise again simultaneously
Continue that raspberry shape PS/SiO will be obtained after stirring 10h2Complex microsphere lotion drying for standby after centrifugal treating.
3) sandwich type PS/SiO2The preparation of/PDA complex microsphere: the raspberry shape PS/SiO prepared in 0.5g step 2 is taken2
Complex microsphere ultrasonic disperse is ethyl alcohol: water=7: 1 in the mixed solvent in 400mL volume ratio, and 1.5g trihydroxy aminomethane is added
With 4.5g dopamine, it is mixed for 24 hours under room temperature, dopamine is in PS/SiO2Sandwich can be obtained in complex microsphere surface aggregate
Type PS/SiO2/ PDA complex microsphere.
4) hollow sandwich type C/SiO2The preparation of/C hybrid microspheres: it with the heating rate of 2 DEG C/min, will be made in step 3)
Standby all sandwich type polystyrene/silica dioxide/poly-dopamine complex microspheres are heated to 800 DEG C and are protected in nitrogen atmosphere
Hollow sandwich type C/SiO can be obtained in warm 2h2/ C hybrid microspheres.
5) preparation of the bivalve layer hollow caged carbosphere of foreign components: all hollow sandwich type C/ that will be prepared in step 4)
SiO2The HF that/C hybrid microspheres are 10wt% with 100mL concentration etches 2h and after centrifuge washing is handled, and it is different that bivalve layer can be obtained
The hollow caged carbosphere of component.
Fig. 1 is the electron scanning micrograph for the bivalve layer hollow caged carbosphere of foreign components that the present embodiment obtains, from
In can find that microsphere surface has large-sized mesoporous or macropore, there are also one layer of carbon shell below hole.Fig. 2 obtains for the present embodiment
The transmission electron microscope photo of the bivalve layer hollow caged carbosphere of foreign components arrived, it can be seen that microballoon is with good
Dispersibility.Fig. 3 is the high-amplification-factor transmission electron microscopy for the bivalve layer hollow caged carbosphere of foreign components that the present embodiment obtains
Mirror photo, it can be seen that microballoon center has hollow cavity, microballoon has inside and outside two layers of shell structure, has on each shell
Large-sized mesoporous or macropore.
Embodiment 2:
1) soft core/hard shell polystyrene (PS) microballoon preparation: 8mL styrene is measured, is added dropwise in 120mL deionized water
In, it is passed through high pure nitrogen stirring 30min, 70 DEG C is heated to, the deionized water solution of 14mL potassium peroxydisulfate containing 0.12g is then added
As initiator, 4h is stirred at 70 DEG C, then in the above system be added 1.8mL divinylbenzene the reaction was continued for 24 hours
Obtain soft core/hard shell PS microballoon that diameter is 280nm.
2) raspberry shape PS/SiO2The preparation of complex microsphere: it is carried out according to embodiment 1.
3) sandwich type PS/SiO2The preparation of/PDA complex microsphere: it is carried out according to embodiment 1.
4) hollow sandwich type C/SiO2The preparation of/C hybrid microspheres: it is carried out according to embodiment 1.
5) it the preparation of the bivalve layer hollow caged carbosphere of foreign components: is carried out according to embodiment 1.
Embodiment 3:
1) soft core/hard shell polystyrene (PS) microballoon preparation: 8mL styrene is measured, is added dropwise in 120mL deionized water
In, it is passed through high pure nitrogen stirring 30min, 70 DEG C is heated to, the deionized water solution of 14mL potassium peroxydisulfate containing 0.08g is then added
As initiator, 4h is stirred at 70 DEG C, then in the above system be added 1.8mL divinylbenzene the reaction was continued for 24 hours
Obtain soft core/hard shell PS microballoon that diameter is 320nm.
2) it the preparation of PS/PDA complex microsphere: is carried out according to embodiment 1.
3) sandwich type PS/SiO2The preparation of/PDA complex microsphere: it is carried out according to embodiment 1.
4) hollow sandwich type C/SiO2The preparation of/C hybrid microspheres: it is carried out according to embodiment 1.
5) it the preparation of the bivalve layer hollow caged carbosphere of foreign components: is carried out according to embodiment 1.
Embodiment 4:
1) it soft core/hard shell polystyrene (PS) microballoon preparation: is carried out according to embodiment 1.
2) raspberry shape PS/SiO2The preparation of complex microsphere: take the PS microballoon ultrasonic disperse that is prepared in 0.5g step 1) in
In 160mL ethyl alcohol, 1mL ethyl orthosilicate is then added into above-mentioned solution and stirs 30min, 15mL ammonium hydroxide is then added dropwise again simultaneously
Continue that raspberry shape PS/SiO will be obtained after stirring 10h2Complex microsphere lotion drying for standby after centrifugal treating.
3) sandwich type PS/SiO2The preparation of/PDA complex microsphere: it is carried out according to embodiment 1.
4) hollow sandwich type C/SiO2The preparation of/C hybrid microspheres: it is carried out according to embodiment 1.
5) it the preparation of the bivalve layer hollow caged carbosphere of foreign components: is carried out according to embodiment 1.
Embodiment 5:
1) it soft core/hard shell polystyrene (PS) microballoon preparation: is carried out according to embodiment 1.
2) raspberry shape PS/SiO2The preparation of complex microsphere: take the PS microballoon ultrasonic disperse that is prepared in 0.5g step 1) in
In 160mL ethyl alcohol, 1mL ethyl orthosilicate is then added into above-mentioned solution and stirs 30min, 25mL ammonium hydroxide is then added dropwise again simultaneously
Continue that raspberry shape PS/SiO will be obtained after stirring 10h2Complex microsphere lotion drying for standby after centrifugal treating.
3) sandwich type PS/SiO2The preparation of/PDA complex microsphere: it is carried out according to embodiment 1.
4) hollow sandwich type C/SiO2The preparation of/C hybrid microspheres: it is carried out according to embodiment 1.
5) it the preparation of the bivalve layer hollow caged carbosphere of foreign components: is carried out according to embodiment 1.
Embodiment 6:
1) it soft core/hard shell polystyrene (PS) microballoon preparation: is carried out according to embodiment 1.
2) raspberry shape PS/SiO2The preparation of complex microsphere: it is carried out according to embodiment 1.
3) sandwich type PS/SiO2The preparation of/PDA complex microsphere: the raspberry shape PS/SiO prepared in 0.5g step 2 is taken2
Complex microsphere ultrasonic disperse is ethyl alcohol: water=7: 1 in the mixed solvent in 400mL volume ratio, and 1.25g trihydroxy amino first is added
Alkane and 3.75g dopamine are mixed for 24 hours under room temperature, and sandwich can be obtained in Surfaces of Polystyrene Microparticles polymerization in dopamine
Type PS/SiO2/ PDA complex microsphere.
4) hollow sandwich type C/SiO2The preparation of/C hybrid microspheres: it is carried out according to embodiment 1.
5) it the preparation of the bivalve layer hollow caged carbosphere of foreign components: is carried out according to embodiment 1.
Embodiment 7:
1) it soft core/hard shell polystyrene (PS) microballoon preparation: is carried out according to embodiment 1.
2) raspberry shape PS/SiO2The preparation of complex microsphere: it is carried out according to embodiment 1.
3) sandwich type PS/SiO2The preparation of/PDA complex microsphere: the raspberry shape PS/SiO prepared in 0.5g step 2 is taken2
Complex microsphere ultrasonic disperse is ethyl alcohol: water=7: 1 in the mixed solvent in 400mL volume ratio, and 1.75g trihydroxy amino first is added
Alkane and 5.25g dopamine are mixed for 24 hours under room temperature, and sandwich can be obtained in Surfaces of Polystyrene Microparticles polymerization in dopamine
Type PS/SiO2/ PDA complex microsphere.
4) hollow sandwich type C/SiO2The preparation of/C hybrid microspheres: it is carried out according to embodiment 1.
5) it the preparation of the bivalve layer hollow caged carbosphere of foreign components: is carried out according to embodiment 1.
Embodiment 8:
1) soft core/hard shell PS microballoon preparation: 8mL styrene is measured, is added dropwise in 120mL deionized water, is passed through high-purity
Nitrogen gas stirring 30min is heated to 70 DEG C, the deionized water solution of 14mL potassium peroxydisulfate containing 0.16g is then added as initiator,
4h is stirred at 70 DEG C, then in the above system be added 3.5mL divinylbenzene the reaction was continued for 24 hours, can be obtained diameter is
The soft core of 275nm/hard shell PS microballoon.
2) raspberry shape PS/SiO2The preparation of complex microsphere: it is carried out according to embodiment 1.
3) sandwich type PS/SiO2The preparation of/PDA complex microsphere: it is carried out according to embodiment 1.
4) hollow sandwich type C/SiO2The preparation of/C hybrid microspheres: it is carried out according to embodiment 1.
5) it the preparation of the bivalve layer hollow caged carbosphere of foreign components: is carried out according to embodiment 1.
Embodiment 9:
1) soft core/hard shell PS microballoon preparation: 8mL styrene is measured, is added dropwise in 120mL deionized water, is passed through high-purity
Nitrogen gas stirring 30min is heated to 70 DEG C, the deionized water solution of 14mL potassium peroxydisulfate containing 0.16g is then added as initiator,
4h is stirred at 70 DEG C, then in the above system be added 5.3mL divinylbenzene the reaction was continued for 24 hours, can be obtained diameter is
The soft core of 290nm/hard shell PS microballoon.
2) raspberry shape PS/SiO2The preparation of complex microsphere: it is carried out according to embodiment 1.
3) sandwich type PS/SiO2The preparation of/PDA complex microsphere: it is carried out according to embodiment 1.
4) hollow sandwich type C/SiO2The preparation of/C hybrid microspheres: it is carried out according to embodiment 1.
5) it the preparation of the bivalve layer hollow caged carbosphere of foreign components: is carried out according to embodiment 1.
The structural parameters of the layer hollow caged carbosphere of foreign components of bivalve made from each embodiment are as shown in table 1.
Examples detailed above shows: in caged carbosphere hollow using each embodiment preparation bivalve layer foreign components, reducing and causes
The dosage of agent can increase soft core/hard shell PS microballoon size, and then increase the cavity size of caged carbosphere, increase crosslinking agent
The dosage of divinylbenzene can increase the thickness of internal layer carbon-coating, and the dosage for increasing ammonium hydroxide can increase nanometer silicon dioxide particle
Diameter leads directly to that large scale is mesoporous or the diameter of macropore to increase on inside and outside carbon shell, and the dosage for increasing dopamine can then increase
The thickness of outer layer carbon shell, to realize the structure regulating to the bivalve layer hollow caged carbosphere of foreign components.
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 (4)
1. a kind of regulatable bivalve layer hollow caged carbosphere of foreign components of structure, which is characterized in that the microballoon ball wall is by inside and outside
Two layers of carbon shell composition, the ingredient of internal layer carbon shell are common carbon material, and the ingredient of outer layer carbon shell is the carbon material of N doping, two layers of carbon
There is straight-through large scale mesoporous on shell or macropore, cavity size, inside and outside shell thickness and two layers of the carbon shell of hollow caged microballoon
On straight-through large scale is mesoporous or the diameter of macropore is adjustable.
2. the layer hollow caged carbosphere of foreign components in bivalve according to claim 1, which is characterized in that the microballoon hollow cavity
Size can be adjusted between 210-550nm.
3. the layer hollow caged carbosphere of foreign components in bivalve according to claim 1, it is characterised in that the microballoon internal layer carbon shell
Thickness can be adjusted between 10-30nm, the thickness of outer layer carbon shell can be adjusted between 35-110nm, ectonexine carbon
Large scale leads directly to mesoporous or macropore diameter and can be adjusted between 35-90nm on shell.
4. the layer of bivalve described in one of -3 hollow caged carbosphere of foreign components according to claim 1, preparation process includes following
Step: 1. soft core/hard shell polystyrene microsphere preparation: a certain amount of styrene is measured, is added dropwise in 120mL deionized water
In, it is passed through high pure nitrogen stirring 30min, is heated to 70 DEG C, a certain amount of deionized water solution containing potassium peroxydisulfate is then added and makees
For initiator, 4h is stirred at 70 DEG C, and a certain amount of cross-linker divinylbenzene is then added in the above system and is reacted
For 24 hours, it can be obtained soft core/hard shell polystyrene microsphere that diameter is 250-600nm；2. raspberry shape polystyrene/silica dioxide
The preparation of complex microsphere: taking a certain amount of step, 1. the middle polystyrene microsphere ultrasonic disperse prepared connects in a certain amount of ethyl alcohol
A certain amount of ethyl orthosilicate is added into above-mentioned solution and stirs 30min, a certain amount of ammonium hydroxide is then added dropwise again and continues
Polystyrene/silica dioxide complex microsphere can be obtained after stirring 10h；3. sandwich type polystyrene/silica dioxide/poly- DOPA
The preparation of amine complex microsphere: a certain amount of step 2. middle raspberry shape polystyrene/silica dioxide complex microsphere ultrasound prepared point is taken
Dissipating in a certain amount of volume ratio is ethyl alcohol: water=7: a certain amount of trihydroxy aminomethane and dopamine is added, often in 1 in the mixed solvent
Temperature is lower to be mixed for 24 hours, and the polyphenyl second of sandwich type can be obtained in the polymerization of polystyrene/silica dioxide microsphere surface for dopamine
Alkene/silica/poly-dopamine organic/inorganic complex microsphere；4. hollow sandwich type C/SiO2The preparation of/C hybrid microspheres: with
The heating rate of 2 DEG C/min, by step, 3. the middle all sandwich type polystyrene/silica dioxide/poly-dopamines prepared are compound
Microballoon is heated to 800 DEG C in nitrogen atmosphere and keeps the temperature 2h, and hollow sandwich type C/SiO can be obtained2/ C hybrid microspheres；5. double
The preparation of the hollow caged carbosphere of shell foreign components: by step 4. in prepare all hollow sandwich type C/SiO2/ C hydridization is micro-
The HF that ball is 10wt% with 100mL concentration etches 2h and after centrifuge washing is handled, and the bivalve layer hollow caged of foreign components can be obtained
Carbosphere.
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| CN114488691A (en) * | 2022-02-28 | 2022-05-13 | 河源诚展科技有限公司 | Photosensitive solder resist dry film and preparation method thereof |
| CN115744876A (en) * | 2022-06-22 | 2023-03-07 | 江苏理工学院 | Synthetic method and application of two-dimensional layered hollow carbon nanoparticle array superstructure |
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| CN113636563B (en) * | 2021-08-24 | 2023-12-22 | 郑州轻工业大学 | SiO (silicon dioxide) 2 Preparation method of incompletely coated magnetic nano particles |
| 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 |
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| CN115744876B (en) * | 2022-06-22 | 2023-12-22 | 江苏理工学院 | Synthesis method and application of two-dimensional layered hollow carbon nanoparticle array superstructure |
| CN117534058A (en) * | 2024-01-04 | 2024-02-09 | 内蒙古大学 | High-specific-surface raspberry-shaped mesoporous carbon ball and preparation method thereof |
| CN117534058B (en) * | 2024-01-04 | 2024-03-29 | 内蒙古大学 | High-specific-surface raspberry-shaped mesoporous carbon ball and preparation method thereof |
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