CN107857249A - A kind of preparation method of N doping annular hollow carbon nano-material - Google Patents
A kind of preparation method of N doping annular hollow carbon nano-material Download PDFInfo
- Publication number
- CN107857249A CN107857249A CN201711182393.2A CN201711182393A CN107857249A CN 107857249 A CN107857249 A CN 107857249A CN 201711182393 A CN201711182393 A CN 201711182393A CN 107857249 A CN107857249 A CN 107857249A
- Authority
- CN
- China
- Prior art keywords
- carbon nano
- annular hollow
- ring
- preparation
- hollow carbon
- 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.)
- Granted
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/01—Crystal-structural characteristics depicted by a TEM-image
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/64—Nanometer sized, i.e. from 1-100 nanometer
Abstract
The present invention provides a kind of preparation method of N doping annular hollow carbon nano-material, belongs to materials science field.Polymer with nitrogen is coated on ring-type C by this method first3N4In template, high-temperature calcination then is carried out to it, high temperature makes C3N4Decompose, produce a large amount of nitrogenous gas, pore creating material and nitrogen source can be used as, while polymer carbonization obtains N doping annular hollow carbon nano-material.The material structure is unique, has high nitrogen-containing, is had broad application prospects in ultracapacitor, lithium ion battery, electrochemical catalyst etc..This method has the characteristics of easy to operate, easy industrialized production and environmental pollution are small, is a kind of preparation method of important N doping annular hollow carbon nano-material.
Description
Technical field
The invention belongs to materials science field, more particularly to a kind of preparation of N doping annular hollow carbon nano-material
Method.
Background technology
Carbon Materials are because heat endurance is good, mechanical stability is high, pore structure is flourishing, excellent electric conductivity, specific surface area are big
The features such as, show huge application potential with fields such as conversions in separation, absorption, catalysis, gas storage and energy storage.Material
The performance of material is mainly made from it and structures shape, and wherein structure is even more important for nano material.At present, people have synthesized
Go out the different carbon nano-material of pattern, such as zero dimension fullerene, one-dimensional CNT, two-dimensional sheet graphene and various three-dimensional groups
It is carbon nano-structured to fill body etc., by the also controllable synthesis nanometer carbon plate of template, ordered mesoporous carbon, hollow carbon shell etc., but closes
The carbon material for closing cyclic structure has no report so far.The ring-type nano material of current rarely seen report has：Nanometer ring-type-Fe2O3
[Xianluo Hu,et al.Advanced Materials,2007,19(17):2324], Au nano-rings [Yan Feng, et
al.Nano Letters,2004,4(7):1193] and TiO2Nano-rings [Sun Fengqiang, et al.Chemistry of
Materials,2006,18(16):3774], but building-up process step is numerous and diverse, and yield is extremely low.Hollow annular nanostructured between
Between one peacekeeping two-dimensional material, due to unique structure, inner and outer surfaces can utilize simultaneously, and specific surface area is big, it is expected to assign material
Excellent performance.
In addition, Heteroatom doping is the further important means for improving Carbon Materials performance.Especially nitrogen-atoms, it can be doped to
In charcoal skeleton, regulate and control its physicochemical properties, so as to strengthen porous carbon material function, or even assign Carbon Materials new function.Grind
Study carefully and show, after introducing nitrogen-atoms in charcoal skeleton, lone pair electrons can assign sp in nitrogen-atoms2Delocalization pi system in hydridization charcoal skeleton
Negative electrical charge, so as to strengthen the electric conductivity of Carbon Materials [Kurak K.A., et al.Journal of Physical Chemistry
C,2009,(113):6730]；The band structure of the controllable Carbon Materials of nitrogen-atoms of electron rich is adulterated, drops the valence band of Carbon Materials
It is low, increase the electron density on Carbon Materials fermi level and strengthen its chemical stability [Kim D.P., et al.Chemistry
of Materials,1991,(3):686].Usually, by the way that nitrogenous forerunner is post-processed or be directly pyrolyzed to carbon material
Body carries out N doping to carbon material.But post-process the current document of nitrogen element content that nitriding (such as ammonia high-temperature heat treatment) introduces
The maximum of report is no more than 10wt.%, and the nitrogen-containing functional group formed is typically unstable, is mainly distributed on carbon material table
Face, it is this surface-functionalized to change most carbon skeleton attribute.And based on the nitrogenous forerunner of directly pyrolysis of template auxiliary
Body method, the porous carbon materials in homogeneous aperture can be not only prepared, while can realize that high content nitrogen element is bulk phase-doped.Conventional mould
Plate agent includes hard template (such as micro-/ nano silicon ball, mesoporous silicon, nickel foam, magnesia) and soft template (such as triblock copolymer),
The rich nitrogen presoma used has various polymer such as polyacrylonitrile, polypyrrole, melamine etc., but the removal step of template compares
Numerous and diverse, agents useful for same corrosivity is strong (strong acid or highly basic etching), and environment certainly will be damaged if prepared by batch.
Therefore, how the annular hollow carbon nano-material of novel structure synthesized by the method for easy green, high-volume,
As a huge challenge.The present invention is developed from sacrifice template, the annular hollow carbon nano-material of nitrogen doped in situ
Environment-friendly, efficient technology of preparing, can undoubtedly fill up the blank of the international and domestic research in carbon material field.
The content of the invention
The invention provides a kind of preparation method of N doping annular hollow carbon nano-material, first by polymer with nitrogen bag
Overlay on ring-type C3N4Surface, high-temperature calcination processing then is carried out to it, high temperature makes C3N4Decompose, produce a large amount of nitrogenous gas, can
As pore creating material and nitrogen source, N doping annular hollow carbon nano-material is simply efficiently obtained.
Technical scheme：
A kind of preparation method of N doping annular hollow carbon nano-material, step are as follows：
(1) by ring-type g-C3N4Template is scattered in a solvent, stirs and ultrasonic, obtains template solution；
(2) polymer with nitrogen monomer is added in template solution, lasting stirring is polymerize and coating reaction, makes nitrogenous poly-
Monomer adduct is coated on ring-type g-C3N4Surface；
Described polymer with nitrogen monomer is dopamine, aniline or pyrroles；
The concentration of described polymer with nitrogen monomer is 0.5-8mg/mL；Polymer with nitrogen monomer and ring-type g-C3N4Template
Mass ratio be 1:1~1:4；
When described polymer with nitrogen monomer is dopamine, other reactions are no longer added during polymerization coating reaction
Thing；
When described polymer with nitrogen monomer is aniline or pyrroles, while aniline or pyrroles is added, also to add
Surfactant, acid and initiator；The concentration of described surfactant is no more than 4mg/mL；Described sour concentration is little
In 3mg/mL；The concentration of described initiator is not more than 0.5mg/mL；
Described polymerization coating reaction temperature is 10-35 DEG C, time 2-96h；
(3) by the solution centrifugal after polymerization and coating reaction, with water and ethanol clean for several times, dry, obtain polymer bag
The ring-type g-C covered3N4；
(4) by the ring-type g-C of polymer overmold3N4It is placed in tube furnace, is calcined under inert gas shielding, is calcined
During ring-type g-C3N4Decompose, while Polymer-pyrolysis polymerize, and is cooled to room temperature after calcining, obtains N doping annular hollow and receive
Rice Carbon Materials.
Ring-type g-C in described step (1)3N4Template is made using chemical vapour deposition technique, and specific method is：With trimerization
Cyanamide is raw material, deposition reaction is carried out by template of nanometer titanium dioxide silicon ball, and sedimentation products are through hf etching, after centrifuge washing
It is freeze-dried to obtain ring-type g-C3N4Template.
Solvent is the one of water, ethanol, ether, acetonitrile, Tris buffer solutions or phosphate buffer solution in described step (1)
Kind or several mixing.
Ring-type g-C in described step (1)3N4The concentration of template in a solvent is 1-8mg/mL, ultrasonic time 10min-
4h。
Surfactant is neopelex, cetyl trimethylammonium bromide, 12 in described step (2)
One or both of sodium alkyl sulfate and polyvinylpyrrolidone (PVP) are mixed above.
Acid is that one or both of hydrochloric acid, sulfuric acid, phytic acid, nitric acid are mixed above in described step (2).
Initiator is Na in described step (2)2SO8、(NH4)2SO8、K2Cr2O7、KIO3、FeCl3、FeCl4、H2O2、Ce
(SO4)2、AlCl3、MnO2, one or both of BPO (benzoyl peroxide) it is mixed above.
Drying temperature is 50-100 DEG C in described step (3), time 12-36h.
Inert gas is that one or both of nitrogen, argon gas, helium are mixed above in described step (4).
Calcining heating rate is 2-10 DEG C/min in described step (4), and temperature is 500-1000 DEG C, time 1-3h.
Described doping annular hollow carbon nano-material has the characteristics that high nitrogen content, unique structure, ultracapacitor,
Lithium ion battery, electrochemical catalyst etc. have potential broad prospect of application.
Beneficial effects of the present invention：
1. template is environmentally friendly, pollution-free；
2. removing template while charing, technique is simple；
3. its thickness of the N doping annular hollow carbon nano-material of preparation can be by template and the ratio or poly- of polymer monomer
Close time control；
4. a large amount of nitrogenous gas are produced during template decomposition can be used as pore creating material and nitrogen source；
5. the N doping annular hollow carbon nano-material nitrogen content prepared is up to 10wt.% through elementary analysis, its nitrogen content
Left and right.
Brief description of the drawings
Fig. 1 is N doping annular hollow carbon nano-material preparation flow figure.
Fig. 2 is the ring-type g-C that prior art is prepared3N4The SEM of template.
Fig. 3 N doping annular hollow carbon nano-materials derived from the dopamine prepared by embodiment 1 (are labeled as PDA-N-
CNRs-3 electron scanning micrograph).
Fig. 4 N doping annular hollow carbon nano-materials derived from the dopamine prepared by embodiment 1 (are labeled as PDA-N-
CNRs-3 transmission electron microscope photo).
Fig. 5 N doping annular hollow carbon nano-materials derived from the dopamine prepared by embodiment 2 (are labeled as PDA-N-
CNRs-1 transmission electron microscope photo).
Fig. 6 is that the N doping annular hollow carbon nano-material of the aniline derivatives prepared by embodiment 3 (is labeled as PANI-N-
CNRs-0.357 electron scanning micrograph).
Fig. 7 is that the N doping annular hollow carbon nano-material of the pyrrole derivatives prepared by embodiment 4 (is labeled as PPy-N-
CNRs-0.338 electron scanning micrograph).
Embodiment
Below in conjunction with accompanying drawing and technical scheme, embodiment of the invention is further illustrated.
The preparation flow schematic diagram of N doping annular hollow carbon nano-material in the present invention, the specific following institute of preparation process
State：
Embodiment 1：
By 100mg ring-types g-C3N4It is dispersed in 50mL Tris buffer solutions (pH=8.5), ultrasound 20 minutes, obtains concentration
For 2mg/mL ring-type g-C3N4Suspension.300mg dopamines are added in aforesaid liquid.After stirring 12h at room temperature, centrifuge, point
Do not cleaned for several times with water and ethanol.After 60 DEG C of dry 36h, by the ring-type g-C of Surface coating poly-dopamine3N4It is placed in corundum boat,
In tube furnace under argon gas atmosphere, with 5 DEG C/min heating rate, 800 DEG C, constant temperature 1h are warming up to, obtains N doping ring-type sky
Heart carbon nano-material (Product Labeling PDA-N-CNRs-3).Fig. 2 show ring-type g-C3N4Stereoscan photograph, present ring
Shape structure and size are homogeneous.Fig. 3 illustrates ESEM of the gained N doping annular hollow carbon nano-material under low power number and shone
Piece, it can be seen that it replicates the pattern of template, is the homogeneous cyclic structure of yardstick.The PDA-N- further shown from Fig. 4
It is hollow-core construction that the high magnification numbe stereoscan photograph of CNRs-3 samples, which can be seen that it, hollow annular diameters about 80nm, and outer shroud is straight
Footpath about 140nm, wall thickness about 6.6nm.
Embodiment 2：
By 100mg ring-types g-C3N4It is dispersed in 50mL Tris buffer solutions (pH=8.5), ultrasound 10 minutes, obtains concentration
For 2mg/mL ring-type g-C3N4Suspension.100mg dopamines are added in aforesaid liquid.After stirring 12h at room temperature, centrifuge, point
Do not cleaned for several times with water and ethanol.After 80 DEG C of dry 24h, by the ring-type g-C of Surface coating poly-dopamine3N4It is placed in corundum boat,
In tube furnace under nitrogen atmosphere, with 10 DEG C/min heating rate, 800 DEG C, constant temperature 1h are warming up to, obtains N doping ring-type sky
Heart carbon nano-material (Product Labeling PDA-N-CNRs-1).The high magnification numbe of the PDA-N-CNRs-1 samples shown from Fig. 5 is swept
It is hollow-core construction to retouch electromicroscopic photograph and can be seen that it, and hollow annular diameters about 100nm, outer annular diameter about 140nm, wall thickness is about
3.7nm。
Embodiment 3：
By 100mg ring-types g-C3N4It is added in 40mL water, stirring and ultrasonic 4h, obtains with 5mg neopelexes
Concentration is 2.5mg/mL ring-type g-C3N4Suspension.Afterwards respectively by 35 μ L aniline, 0.25mL phytic acid (25%), 110mg over cures
Sour ammonium is added in aforesaid liquid.After stirring 2h at room temperature, centrifugation, cleaned for several times with water and ethanol respectively.After 100 DEG C of dry 12h,
By the ring-type g-C of Surface coating polyaniline3N4It is placed in corundum boat, in tube furnace under argon gas atmosphere, with 5 DEG C/min heating
Speed, 600 DEG C, constant temperature 2h are warming up to, obtain N doping annular hollow carbon nano-material (Product Labeling PANI-N-CNRs-
0.357).Fig. 6 show sweeping for N doping annular hollow carbon nano-material PANI-N-CNRs-0.357 samples derived from polyaniline
Retouch sem image, it can be seen that it replicates the pattern of template, keeps the annular hollow structure of size uniformity.
Embodiment 4：
By 100mg ring-types g-C3N4It is added in 40mL water, stirring and ultrasonic 2h, obtains with 5mg neopelexes
Concentration is 2.5mg/mL ring-type g-C3N4Suspension.Afterwards respectively by 35 μ L pyrroles, 1mL hydrochloric acid (0.1mol/L), 110mg mistakes
Ammonium sulfate is added in aforesaid liquid.After stirring 2h at room temperature, centrifugation, cleaned for several times with water and ethanol respectively.100 DEG C of dry 12h
Afterwards, by the ring-type g-C of Surface coating polypyrrole3N4It is placed in corundum boat, in tube furnace under helium atmosphere, with 2 DEG C/min liter
Warm speed, 900 DEG C, constant temperature 1h are warming up to, obtain N doping annular hollow carbon nano-material (Product Labeling PPy-N-CNRs-
0.338).Fig. 7 show sweeping for N doping annular hollow carbon nano-material PPy-N-CNRs-0.338 samples derived from polypyrrole
Retouch electromicroscopic photograph, it can be seen that it replicates the pattern of template, keeps the annular hollow structure of size uniformity.
Claims (9)
1. a kind of preparation method of N doping annular hollow carbon nano-material, it is characterised in that step is as follows：
(1) by ring-type g-C3N4Template is scattered in a solvent, stirs and ultrasonic, obtains template solution；
Described ring-type g-C3N4The concentration of template in a solvent is 1-8mg/mL, ultrasonic time 10min-4h；
(2) polymer with nitrogen monomer is added in template solution, lasting stirring is polymerize and coating reaction, makes polymer with nitrogen
Monomer is coated on ring-type g-C3N4Surface；
Described polymer with nitrogen monomer is dopamine, aniline or pyrroles；
The concentration of described polymer with nitrogen monomer is 0.5-8mg/mL；Polymer with nitrogen monomer and ring-type g-C3N4The matter of template
Amount is than being 1:1~1:4；
When described polymer with nitrogen monomer is dopamine, other reactants are no longer added during polymerization coating reaction；
When described polymer with nitrogen monomer is aniline or pyrroles, while aniline or pyrroles is added, surface is also added
Activating agent, acid and initiator；The concentration of described surfactant is no more than 4mg/mL；Described sour concentration is not more than
3mg/mL；The concentration of described initiator is not more than 0.5mg/mL；
Described polymerization coating reaction temperature is 10-35 DEG C, time 2-96h；
(3) by the solution centrifugal after polymerization and coating reaction, with water and ethanol clean for several times, dry, obtain polymer overmold
Ring-type g-C3N4；
(4) by the ring-type g-C of polymer overmold3N4It is placed in tube furnace, is calcined under inert gas shielding, calcination process
Middle ring-type g-C3N4Decompose, while Polymer-pyrolysis polymerize, and is cooled to room temperature after calcining, obtains N doping annular hollow Nano carbon
Material；
Described calcining heating rate is 2-10 DEG C/min, and temperature is 500-1000 DEG C, time 1-3h.
A kind of 2. preparation method of N doping annular hollow carbon nano-material according to claim 1, it is characterised in that institute
Ring-type g-C in the step of stating (1)3N4Template is made using chemical vapour deposition technique, and specific method is：Using melamine as raw material,
Deposition reaction is carried out by template of nanometer titanium dioxide silicon ball, sedimentation products are through hf etching, through freeze-drying after centrifuge washing
Obtain ring-type g-C3N4Template；Solvent is that water, ethanol, ether, acetonitrile, Tris buffer solutions or phosphate delay in described step (1)
Rush one or more kinds of mixing of solution.
3. a kind of preparation method of N doping annular hollow carbon nano-material according to claim 1 or 2, its feature exist
In surfactant is neopelex, cetyl trimethylammonium bromide, dodecyl in described step (2)
One or both of sodium sulphate and polyvinylpyrrolidone are mixed above；Described acid is in hydrochloric acid, sulfuric acid, phytic acid, nitric acid
One or more kinds of mixing；Described initiator is Na2SO8、(NH4)2SO8、K2Cr2O7、KIO3、FeCl3、FeCl4、
H2O2、Ce(SO4)2、AlCl3、MnO2, one or both of benzoyl peroxide it is mixed above.
4. a kind of preparation method of N doping annular hollow carbon nano-material according to claim 1 or 2, its feature exist
In drying temperature is 50-100 DEG C in described step (3), time 12-36h.
A kind of 5. preparation method of N doping annular hollow carbon nano-material according to claim 3, it is characterised in that institute
Drying temperature is 50-100 DEG C in the step of stating (3), time 12-36h.
6. a kind of preparation method of N doping annular hollow carbon nano-material according to claim 1,2 or 5, its feature exist
In inert gas is that one or both of nitrogen, argon gas, helium are mixed above in described step (4).
A kind of 7. preparation method of N doping annular hollow carbon nano-material according to claim 3, it is characterised in that institute
Inert gas is that one or both of nitrogen, argon gas, helium are mixed above in the step of stating (4).
A kind of 8. preparation method of N doping annular hollow carbon nano-material according to claim 4, it is characterised in that institute
Inert gas is that one or both of nitrogen, argon gas, helium are mixed above in the step of stating (4).
9. the N doping ring-type that the preparation method of any N doping annular hollow carbon nano-materials of claim 1-8 obtains is empty
Heart carbon nano-material is applied to ultracapacitor, lithium ion battery, electrochemical catalyst.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711182393.2A CN107857249B (en) | 2017-11-23 | 2017-11-23 | Preparation method of nitrogen-doped annular hollow nano carbon material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711182393.2A CN107857249B (en) | 2017-11-23 | 2017-11-23 | Preparation method of nitrogen-doped annular hollow nano carbon material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN107857249A true CN107857249A (en) | 2018-03-30 |
| CN107857249B CN107857249B (en) | 2020-06-16 |
Family
ID=61702549
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201711182393.2A Active CN107857249B (en) | 2017-11-23 | 2017-11-23 | Preparation method of nitrogen-doped annular hollow nano carbon material |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN107857249B (en) |
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108394888A (en) * | 2018-04-09 | 2018-08-14 | 安徽大学 | A kind of preparation method of N doping meso-porous hollow Nano carbon balls |
| CN108493461A (en) * | 2018-05-08 | 2018-09-04 | 大连理工大学 | A kind of N adulterates the catalyst and preparation method thereof of porous carbon coating Fe, Co bimetal nano particles |
| CN109136979A (en) * | 2018-08-08 | 2019-01-04 | 东华大学 | The nitrogen-doped carbon composite material of hollow zinc doping cobalt oxide nickel coated and its preparation |
| CN109126683A (en) * | 2018-09-11 | 2019-01-04 | 哈尔滨工程大学 | A kind of modified C3N4The preparation method of material |
| CN109437156A (en) * | 2018-11-13 | 2019-03-08 | 上海师范大学 | A kind of preparation method of nitrogen-doped carbon nanometer pipe |
| CN110289179A (en) * | 2019-05-29 | 2019-09-27 | 南京源恒能源科技有限公司 | Reactive metal oxides-carbonization bacteria cellulose electrode material preparation method |
| CN111864193A (en) * | 2019-04-30 | 2020-10-30 | 中国科学院上海硅酸盐研究所 | Heteroatom modified hollow micro carbon sphere, preparation method thereof and application thereof in lithium-sulfur battery anode material |
| CN112499615A (en) * | 2020-12-01 | 2021-03-16 | 大连理工大学 | Nano polymer ring, nano carbon ring and preparation method thereof |
| CN113651313A (en) * | 2021-09-28 | 2021-11-16 | 绍兴道普新材料科技有限公司 | Hollow submicron nitrogen-doped carbon tube and preparation method thereof |
| CN113668012A (en) * | 2021-08-12 | 2021-11-19 | 中国石油大学(北京) | Iron/ruthenium nitrogen-doped porous carbon electrocatalyst and preparation method and application thereof |
| CN116377473A (en) * | 2023-03-17 | 2023-07-04 | 大连理工大学 | Nitrogen-doped hollow carbon nano-ring-loaded metal monoatomic material, preparation method and application thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2012250884A (en) * | 2011-06-03 | 2012-12-20 | National Institute For Materials Science | Porous carbon nitride film, method of manufacturing the same, and application using the same |
| CN104961121A (en) * | 2015-06-24 | 2015-10-07 | 上海大学 | Preparation method for nitrogen-doped nuclear shell hollow carbon |
| CN105776174A (en) * | 2016-02-06 | 2016-07-20 | 中国科学院理化技术研究所 | Nitrogen-doped porous carbon nanosheet and preparing method and application thereof |
| CN105948045A (en) * | 2016-07-18 | 2016-09-21 | 湘潭大学 | Preparation method and application of nitrogen-doped starch-based activated carbon microsphere material |
| CN107151003A (en) * | 2017-04-28 | 2017-09-12 | 大连理工大学 | A kind of graphite phase carbon nitride nanometer ring material and preparation method thereof |
-
2017
- 2017-11-23 CN CN201711182393.2A patent/CN107857249B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2012250884A (en) * | 2011-06-03 | 2012-12-20 | National Institute For Materials Science | Porous carbon nitride film, method of manufacturing the same, and application using the same |
| CN104961121A (en) * | 2015-06-24 | 2015-10-07 | 上海大学 | Preparation method for nitrogen-doped nuclear shell hollow carbon |
| CN105776174A (en) * | 2016-02-06 | 2016-07-20 | 中国科学院理化技术研究所 | Nitrogen-doped porous carbon nanosheet and preparing method and application thereof |
| CN105948045A (en) * | 2016-07-18 | 2016-09-21 | 湘潭大学 | Preparation method and application of nitrogen-doped starch-based activated carbon microsphere material |
| CN107151003A (en) * | 2017-04-28 | 2017-09-12 | 大连理工大学 | A kind of graphite phase carbon nitride nanometer ring material and preparation method thereof |
Cited By (17)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108394888A (en) * | 2018-04-09 | 2018-08-14 | 安徽大学 | A kind of preparation method of N doping meso-porous hollow Nano carbon balls |
| CN108493461A (en) * | 2018-05-08 | 2018-09-04 | 大连理工大学 | A kind of N adulterates the catalyst and preparation method thereof of porous carbon coating Fe, Co bimetal nano particles |
| CN109136979A (en) * | 2018-08-08 | 2019-01-04 | 东华大学 | The nitrogen-doped carbon composite material of hollow zinc doping cobalt oxide nickel coated and its preparation |
| CN109126683B (en) * | 2018-09-11 | 2021-06-25 | 哈尔滨工程大学 | Modified C3N4Method for producing a material |
| CN109126683A (en) * | 2018-09-11 | 2019-01-04 | 哈尔滨工程大学 | A kind of modified C3N4The preparation method of material |
| CN109437156A (en) * | 2018-11-13 | 2019-03-08 | 上海师范大学 | A kind of preparation method of nitrogen-doped carbon nanometer pipe |
| CN109437156B (en) * | 2018-11-13 | 2022-01-14 | 上海师范大学 | Preparation method of nitrogen-doped carbon nanotube |
| CN111864193A (en) * | 2019-04-30 | 2020-10-30 | 中国科学院上海硅酸盐研究所 | Heteroatom modified hollow micro carbon sphere, preparation method thereof and application thereof in lithium-sulfur battery anode material |
| CN111864193B (en) * | 2019-04-30 | 2021-10-01 | 中国科学院上海硅酸盐研究所 | Heteroatom modified hollow micro carbon sphere, preparation method thereof and application thereof in lithium-sulfur battery anode material |
| CN110289179A (en) * | 2019-05-29 | 2019-09-27 | 南京源恒能源科技有限公司 | Reactive metal oxides-carbonization bacteria cellulose electrode material preparation method |
| CN112499615A (en) * | 2020-12-01 | 2021-03-16 | 大连理工大学 | Nano polymer ring, nano carbon ring and preparation method thereof |
| CN113668012A (en) * | 2021-08-12 | 2021-11-19 | 中国石油大学(北京) | Iron/ruthenium nitrogen-doped porous carbon electrocatalyst and preparation method and application thereof |
| CN113668012B (en) * | 2021-08-12 | 2022-07-12 | 中国石油大学(北京) | Iron/ruthenium nitrogen-doped porous carbon electrocatalyst and preparation method and application thereof |
| CN113651313A (en) * | 2021-09-28 | 2021-11-16 | 绍兴道普新材料科技有限公司 | Hollow submicron nitrogen-doped carbon tube and preparation method thereof |
| CN113651313B (en) * | 2021-09-28 | 2023-06-06 | 绍兴道普新材料科技有限公司 | Hollow submicron nitrogen-doped carbon tube and preparation method thereof |
| CN116377473A (en) * | 2023-03-17 | 2023-07-04 | 大连理工大学 | Nitrogen-doped hollow carbon nano-ring-loaded metal monoatomic material, preparation method and application thereof |
| CN116377473B (en) * | 2023-03-17 | 2023-11-07 | 大连理工大学 | Nitrogen-doped hollow carbon nano-ring-loaded metal monoatomic material, preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN107857249B (en) | 2020-06-16 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN107857249A (en) | A kind of preparation method of N doping annular hollow carbon nano-material | |
| CN106185937B (en) | A kind of preparation method of carbon nano-particle/two-dimensional layer carbonization titanium composite material | |
| CN106207108B (en) | Si-C composite material and the preparation method and application thereof based on macromolecule foaming microballoon | |
| CN104045077B (en) | The three-dimensional classifying porous Carbon Materials of a kind of Graphene and preparation method | |
| US10115497B2 (en) | Compressive graphene hydrogel and preparation method therefor | |
| CN105126876B (en) | A kind of flower-shaped carbon load MoS2Composite of nano particle and preparation method thereof | |
| EP2660192A1 (en) | Graphene ramification-carbon nanotube composite material and preparation method thereof | |
| CN107622879B (en) | Preparation method of nitrogen-doped graphene/carbon nanotube aerogel electrode | |
| CN102989497B (en) | Mesoporous graphite type carbon nitride/nitrogen-doped graphene composite material and preparation method thereof | |
| CN106356204B (en) | A kind of carbon-based composite electrode material and preparation method thereof | |
| CN106450219B (en) | A kind of three-dimensional vanadium trioxide/carbon composite nano-material and its preparation method and application of various dimensions assembling | |
| CN109728287B (en) | One-dimensional coaxial double-nanotube composite material and preparation method and application thereof | |
| CN104103829B (en) | MoS2Nanometer sheet/graphene composite nano material with holes and preparation method | |
| CN106910640A (en) | Controllable graphene nanometer sheet electrode material of a kind of form and its preparation method and application | |
| CN108831757B (en) | A kind of preparation method of N and S codope graphene/carbon nano-tube aeroge | |
| CN107195470B (en) | The nanotube-shaped composite material and preparation method of nickel cobalt iron ternary metal oxide | |
| CN106024410A (en) | High-capacity graphene-based supercapacitor electrode material and preparation method thereof | |
| CN105731446A (en) | Preparation method and product of ultrahigh-specific-area sulphur-nitrogen-co-doped porous graphene | |
| CN109052378B (en) | Preparation method of cobalt-modified nitrogen-doped graphene nanoribbon | |
| CN106057498A (en) | Preparation method and application of molybdenum disulfide/polypyrrole supercapacitor electrode material | |
| CN110165209A (en) | A kind of organic alkali expands layer Mxene material and preparation method thereof, application | |
| CN108597891A (en) | Composite material and preparation method and application are covered in a kind of double load double-contractings of silica@metal oxides/graphene aerogel | |
| Chen et al. | Synthesis of nitrogen-doped hierarchical porous carbon for supercapacitors | |
| CN113880876A (en) | Self-crosslinking graphene dispersing agent, preparation method thereof and nano carbon material dispersion liquid | |
| CN111804313B (en) | Fe 2 O 3 @Co 9 S 8 Preparation method and application of double-hollow core-shell structure nano composite material |
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 | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |