CN105621390A - Preparation method of heteroatom-doped carbon hollow microspheres - Google Patents
Preparation method of heteroatom-doped carbon hollow microspheres Download PDFInfo
- Publication number
- CN105621390A CN105621390A CN201511026909.5A CN201511026909A CN105621390A CN 105621390 A CN105621390 A CN 105621390A CN 201511026909 A CN201511026909 A CN 201511026909A CN 105621390 A CN105621390 A CN 105621390A
- Authority
- CN
- China
- Prior art keywords
- preparation
- heteroatom
- heteroatom doping
- tiny balloon
- under nitrogen
- 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
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- 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
- C01P2004/04—Particle morphology depicted by an image obtained by TEM, STEM, STM or AFM
-
- 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
- C01P2004/62—Submicrometer sized, i.e. from 0.1-1 micrometer
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/12—Surface area
Abstract
The invention provides heteroatom-doped carbon hollow microspheres and a preparation method of the heteroatom-doped carbon hollow microspheres, and belongs to the field of an inorganic carbon nanotechnology. Polyphosphazene microspheres are prepared and then are carbonized under the protection of nitrogen gas to prepare the heteroatom-doped carbon hollow microspheres. A template does not need to be added and only one-step carbonization is needed, so that the problems in the prior art that a process is complicated, the content of heteroatoms is low, the template is needed, the yield is low and the like are solved. The heteroatom-doped carbon hollow microspheres prepared by the invention is high in content and developed in porosity, and can be widely applied to the fields of catalyst carriers, electrochemical energy storage and the like.
Description
Technical field
What the present invention relates to is the technology of a kind of inorganic carbon nm regime, specifically the preparation method of a kind of Heteroatom doping carbon tiny balloon.
Background technology
Carbon hollow ball has that density is low, intrinsic damp performance is good, thermostability and chemically stable good high, specific surface area is controlled and the performance of the multiple excellence such as good biocompatibility, have broad application prospects in fields such as lightweight structural material, metal matrix damping material, support of the catalyst, electrode material for super capacitor, cathode material for lithium ion battery. The new unique property that carbon material causes due to doping heteroatoms so that the carbon hollow ball of Heteroatom doping has more excellent performance. But at present Heteroatom doping carbon hollow ball exist complicated process of preparation, content of heteroatoms low, need the problems such as template, product rate are low.
Through the retrieval of prior art is found, Chinese patent literature CN103395773, publication date 2013-11-20 discloses a kind of Nano carbon hollow sphere and its preparation method, comprising: be on the unsettled silver nitrate solution liquid level in closed reactor of acetylene black of 20-50nm by particle diameter; Acetylene black, to 100-180 DEG C, is carried out being oxidized 2-12 hour by reacting by heating still with the nitric acid vapor produced; Reaction product is washed, dry carbon hollow ball. But it is raw material that prior art had both needed by the acetylene black of 20-50nm, needing again to be oxidized with nitric acid, complex process, product rate is low. The prior art can only obtain carbon hollow ball simultaneously, cannot obtain the carbon hollow ball of Heteroatom doping.
Chinese patent literature CN103613085A, publication date 2014-03-05 discloses Carbon hollow sphere material and its preparation method of a kind of hierarchical porous structure, comprise: use sol-gel method that carbon matrix precursor is coated on template surface, add pore-forming material simultaneously, dissolve and be scattered in water; Mixed solution is put into baking oven gel and obtains presoma; Presoma is carried out high temperature sintering, obtains having the Carbon hollow sphere material of hierarchical porous structure. But the prior art not only needs to use template, in addition it is also necessary to add pore-forming material, not only complex process, and contaminate environment. The prior art also can only obtain carbon hollow ball simultaneously, cannot obtain the carbon hollow ball of Heteroatom doping.
Chinese patent literature CN102583312A, open (bulletin) day 2012.07.18, discloses a kind of nitrogen, the preparation method of phosphorus doping porous carbon ball and application. Take water as solvent, by poly (organophosphazenes) microsphere with activator with (0.2��2): 1 mass ratio mixes, the concentration keeping poly (organophosphazenes) microsphere is 10��30wt%, fully stir, then centrifugation obtains poly (organophosphazenes) microsphere and activating mixtures, finally, poly (organophosphazenes) microsphere and activating mixtures are carried out carbonization and namely obtain nitrogen, phosphorus doping porous carbon ball; Wherein said activator is potassium hydroxide, sodium hydroxide, calcium chloride or zinc chloride. This technology only can obtain solid construction carbosphere, simultaneously, its preparation process employs activator, add last handling process, make complicated process of preparation, in addition such as Chinese patent literature CN200910054594.3, open (disclosing) day 2010.1.27, disclosing the preparation method of a kind of silicon/porous carbon nano-composite particle, the method only obtains the nucleocapsid structure system being made up of silicon and porous carbon.
Summary of the invention
The present invention is directed to prior art above shortcomings, the preparation method of a kind of Heteroatom doping carbon tiny balloon is proposed, it is that comonomer prepares novel polyphosphazene microballoon by selecting Phloroglucinol and hexachlorocyclotriphosphazene, taking this polyphosphonitrile micron ball as presoma, directly obtains through a step charing. This preparation method, without the need to adding template, only through simply carbonizing, prepared carbon tiny balloon content of heteroatoms height, need to include even mesoporous structure and size equal. The carbon tiny balloon of the present invention can be widely used in the fields such as support of the catalyst, electrode material for super capacitor, cathode material for lithium ion battery.
The present invention is achieved by the following technical solutions:
The present invention relates to the preparation method of a kind of Heteroatom doping carbon tiny balloon, selecting hexachlorocyclotriphosphazene and Phloroglucinol to be the polyphosphazenes micron-sphere that comonomer preparation obtains is raw material, heats carbonization under nitrogen protection and prepare in charring furnace.
Described polyphosphazenes micron-sphere prepares in the following manner: is dissolved in organic solvent by hexachlorocyclotriphosphazene and Phloroglucinol, adds triethylamine and fully react after heating, and reaction obtains after product centrifuge washing after terminating.
Described heating carbonization refers to: under nitrogen protection charring furnace is warmed up to 600 DEG C, is incubated 0-3 hour; Continue to be warmed up to 700-1300 DEG C by charring furnace under nitrogen protection, it is incubated 0-6 hour; Under nitrogen protection charring furnace is cooled to room temperature, obtain Heteroatom doping carbon tiny balloon.
Described continuation heats up, and its heat-up rate is 0.2-20 DEG C/min.
The present invention relates to the Heteroatom doping carbon tiny balloon that aforesaid method prepares, its external diameter is 200��800nm, and wall thickness is 30��90nm, and specific surface area is 150��1000m2/ g, porosity is 0.1��0.6cm3/g��
The present invention relates to the application of the Heteroatom doping carbon tiny balloon that aforesaid method prepares, use it for preparation support of the catalyst, electrode material for super capacitor or cathode material for lithium ion battery.
Technique effect
Compared with prior art, the present invention adopts polyphosphazene microspheres to be presoma, and it is at room temperature directly synthesized by single step reaction, and technique is simple, product rate height. Owing to polyphosphazene microspheres itself is containing elements such as nitrogen, oxygen, phosphorus, sulphur, it is part effusion in carbonization process, and another part remains in carbon hollow ball, obtains the carbon tiny balloon of Heteroatom doping. Doping heteroatoms gives carbon hollow ball new special performance so that the carbon hollow ball preparing Heteroatom doping has more excellent performance.
Accompanying drawing explanation
Fig. 1 is the transmission electron microscope photo of the carbon hollow ball prepared in embodiment 1 condition;
Fig. 2 is the results of elemental analyses schematic diagram of the carbon hollow ball prepared in embodiment 1 condition;
Fig. 3 is pore size distribution curve (a) and N2 adsorption-desorption curve (b) schematic diagram of the carbon hollow ball prepared in embodiment 1 condition.
Embodiment
Embodiment 1
The present embodiment realizes the preparation of the hollow carbosphere of Heteroatom doping by following step:
Step one: taking 62.5mg hexachlorocyclotriphosphazene and 45.3mg Phloroglucinol in 100mL round-bottomed flask, add 50mL acetonitrile, ultrasonic disperse is even. Control ultrasonic power is 190W, and temperature of reaction is 30 DEG C, adds 2mL triethylamine, reacts 3 hours. Reaction is centrifugal by product after terminating, and with ethanol and deionized water wash three times, obtains polyphosphazenes micron-sphere.
Step 2: quantitative polyphosphazene microspheres is placed in tubular type charring furnace, vacuumize rear inflated with nitrogen, with the air got rid of in passage, then 600 DEG C slowly it are warming up to the heat-up rate of 2 DEG C/min, constant temperature 1 hour, then continue to be increased to 900 DEG C with the temperature rise rate of 2 DEG C/min, it is incubated Temperature fall after 5 hours and, to room temperature, obtains the hollow carbosphere of Heteroatom doping as depicted in figs. 1 and 2.
The carbon hollow ball N2 adsorption that table 1 is prepared for the present embodiment condition--desorption general data
Embodiment 2
The present embodiment realizes the preparation of the hollow carbosphere of Heteroatom doping by following step:
Step one: getting 62.5mg hexachlorocyclotriphosphazene and 45.3mg Phloroglucinol in 100mL round-bottomed flask, add 50mL acetonitrile, ultrasonic disperse is even. Control ultrasonic power is 190W, and temperature of reaction is 60 DEG C, adds 2mL triethylamine, reacts 3 hours. Reaction is centrifugal by product after terminating, and with ethanol and deionized water wash three times, obtains polyphosphazenes micron-sphere.
Step 2: quantitative polyphosphazene microspheres is placed in tubular type charring furnace, vacuumize rear inflated with nitrogen, with the air got rid of in passage, then 600 DEG C slowly it are warming up to the heat-up rate of 2 DEG C/min, constant temperature 1 hour, then continue to be increased to 1000 DEG C with the temperature rise rate of 2 DEG C/min, it is incubated Temperature fall after 5 hours and, to room temperature, obtains the hollow carbosphere of Heteroatom doping.
The carbon hollow ball N2 adsorption that table 2 is prepared for the present embodiment condition--desorption general data
Embodiment 3
The present embodiment realizes the preparation of the hollow carbosphere of Heteroatom doping by following step:
Step one: getting 62.5mg hexachlorocyclotriphosphazene and 45.3mg Phloroglucinol in 100mL round-bottomed flask, add 50mL acetonitrile, ultrasonic disperse is even. Control ultrasonic power is 190W, and temperature of reaction is 60 DEG C, adds 2mL triethylamine, reacts 3 hours. Reaction is centrifugal by product after terminating, and with ethanol and deionized water wash three times, obtains polyphosphazenes micron-sphere.
Step 2: quantitative polyphosphazene microspheres is placed in tubular type charring furnace, vacuumize rear inflated with nitrogen, with the air got rid of in passage, then 600 DEG C slowly it are warming up to the heat-up rate of 2 DEG C/min, constant temperature 3 hours, then continue to be increased to 1000 DEG C with the temperature rise rate of 5 DEG C/min, it is incubated Temperature fall after 2 hours and, to room temperature, obtains the hollow carbosphere of Heteroatom doping.
The carbon hollow ball N2 adsorption that table 3 is prepared for the present embodiment condition--desorption general data
It can be carried out local directed complete set by those skilled in the art in a different manner by above-mentioned concrete enforcement under the prerequisite not deviating from the principle of the invention and objective; protection scope of the present invention is as the criterion with claim book and can't help above-mentioned concrete enforcement and limit, and each implementation within the scope of it is all by the constraint of the present invention.
Claims (6)
1. the preparation method of a Heteroatom doping carbon tiny balloon, it is characterised in that, selecting hexachlorocyclotriphosphazene and Phloroglucinol to be the polyphosphazenes micron-sphere that comonomer preparation obtains is raw material, heats carbonization under nitrogen protection and prepare in charring furnace.
2. method according to claim 1, it is characterized in that, described polyphosphazenes micron-sphere prepares in the following manner: is dissolved in organic solvent by hexachlorocyclotriphosphazene and Phloroglucinol, adds triethylamine and fully react after heating, and reaction obtains after product centrifuge washing after terminating.
3. method according to claim 1, is characterized in that, described heating carbonization refers to: under nitrogen protection charring furnace is warmed up to 600 DEG C, is incubated 0-3 hour; Continue to be warmed up to 700-1300 DEG C by charring furnace under nitrogen protection, it is incubated 0-6 hour; Under nitrogen protection charring furnace is cooled to room temperature, obtain Heteroatom doping carbon tiny balloon.
4. method according to claim 3, is characterized in that, described continuation heats up, and its heat-up rate is 0.2-20 DEG C/min.
5. the Heteroatom doping carbon tiny balloon that a method according to above-mentioned any claim prepares, it is characterised in that, its external diameter is 200��800nm, and wall thickness is 30��90nm, and specific surface area is 150��1000m2/ g, porosity is 0.1��0.6cm3/g��
6. the application according to the Heteroatom doping carbon tiny balloon described in above-mentioned any claim, it is characterised in that, use it for preparation support of the catalyst, electrode material for super capacitor or cathode material for lithium ion battery.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201511026909.5A CN105621390A (en) | 2015-12-31 | 2015-12-31 | Preparation method of heteroatom-doped carbon hollow microspheres |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201511026909.5A CN105621390A (en) | 2015-12-31 | 2015-12-31 | Preparation method of heteroatom-doped carbon hollow microspheres |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN105621390A true CN105621390A (en) | 2016-06-01 |
Family
ID=56036799
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201511026909.5A Pending CN105621390A (en) | 2015-12-31 | 2015-12-31 | Preparation method of heteroatom-doped carbon hollow microspheres |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105621390A (en) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106000438A (en) * | 2016-06-03 | 2016-10-12 | 兰州交通大学 | Preparation method and application of nitrogen and phosphorus co-doped porous carbon materials |
| CN106744794A (en) * | 2016-12-07 | 2017-05-31 | 温州大学 | A kind of sheet nitrogen-phosphor codoping porous carbon materials and preparation method thereof and purposes |
| CN107601452A (en) * | 2017-10-13 | 2018-01-19 | 厦门大学 | A kind of preparation method of phosphorous porous nano carbon ball |
| CN107673323A (en) * | 2017-11-21 | 2018-02-09 | 中原工学院 | A kind of method that self-template prepares hollow carbon balls |
| CN113135569A (en) * | 2021-05-31 | 2021-07-20 | 东北林业大学 | Biomass-derived grade porous carbon electrode material 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 |
| CN115595183A (en) * | 2022-10-12 | 2023-01-13 | 上海交通大学（Cn） | Sustainable aviation fuel-based nanofluid fuel and implementation method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN103896246A (en) * | 2014-02-19 | 2014-07-02 | 上海交通大学 | Preparation method and application of heteroatom-doped porous carbon nano-tube |
-
2015
- 2015-12-31 CN CN201511026909.5A patent/CN105621390A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN103896246A (en) * | 2014-02-19 | 2014-07-02 | 上海交通大学 | Preparation method and application of heteroatom-doped porous carbon nano-tube |
Non-Patent Citations (1)
| Title |
|---|
| 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 (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106000438A (en) * | 2016-06-03 | 2016-10-12 | 兰州交通大学 | Preparation method and application of nitrogen and phosphorus co-doped porous carbon materials |
| CN106744794A (en) * | 2016-12-07 | 2017-05-31 | 温州大学 | A kind of sheet nitrogen-phosphor codoping porous carbon materials and preparation method thereof and purposes |
| WO2018103386A1 (en) * | 2016-12-07 | 2018-06-14 | 温州大学 | Sheet-shaped nitrogen-phosphorus co-doped porous carbon material and method for preparation thereof and use thereof |
| CN106744794B (en) * | 2016-12-07 | 2018-11-30 | 温州大学 | A kind of sheet nitrogen-phosphor codoping porous carbon materials and preparation method thereof and purposes |
| US10889497B2 (en) | 2016-12-07 | 2021-01-12 | Wenzhou University | Sheet-shaped nitrogen-phosphorus co-doped porous carbon material and method for preparation thereof and use thereof |
| CN107601452A (en) * | 2017-10-13 | 2018-01-19 | 厦门大学 | A kind of preparation method of phosphorous porous nano carbon ball |
| CN107601452B (en) * | 2017-10-13 | 2019-07-23 | 厦门大学 | A kind of preparation method of phosphorous porous nano carbon ball |
| CN107673323A (en) * | 2017-11-21 | 2018-02-09 | 中原工学院 | A kind of method that self-template prepares hollow carbon balls |
| CN113135569A (en) * | 2021-05-31 | 2021-07-20 | 东北林业大学 | Biomass-derived grade porous carbon electrode material 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 |
| CN115595183A (en) * | 2022-10-12 | 2023-01-13 | 上海交通大学（Cn） | Sustainable aviation fuel-based nanofluid fuel and implementation method thereof |
| CN115595183B (en) * | 2022-10-12 | 2023-10-20 | 上海交通大学 | Sustainable aviation fuel-based nanofluid fuel and implementation method thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105621390A (en) | Preparation method of heteroatom-doped carbon hollow microspheres | |
| CN105523541B (en) | Porous carbon tiny balloon of Heteroatom doping and preparation method thereof | |
| CN106629655A (en) | Application and preparation method of biomass-based nitrogen-doped porous carbon | |
| CN105870425B (en) | A kind of Carbon negative electrode material of sodium ion battery and preparation method thereof | |
| CN108232369A (en) | A kind of integrated form flexible electrode of biomass derived and preparation method thereof | |
| CN109801792B (en) | Preparation method and application of carbon-coated iron oxide electrode material | |
| CN108264037B (en) | Three-dimensional porous nitrogen-doped graphene answers the preparation method of material and nitrogen-doped graphene | |
| CN103641100B (en) | Preparation method of cassava-starch-based grading-pore carbon microsphere material | |
| CN108190853B (en) | Preparation method of honeycomb foam wall hollow carbon ball | |
| CN109243862B (en) | Dual-modified carbon hollow sphere compound and preparation method and application thereof | |
| CN108767272A (en) | A kind of nitrogen co-doped porous carbon materials of cobalt and its preparation and application | |
| CN108163833A (en) | A kind of method for preparing the mesoporous carbon nanomaterial of sulfur doping class graphene | |
| CN110492083A (en) | A kind of preparation method of molybdenum disulfide/graphene/carbon multistage hole composite material | |
| CN109065851A (en) | A kind of sulphur carbon composite anode material and preparation method thereof | |
| CN109786711A (en) | A kind of preparation method of porous carbon skeleton cladding tin combination electrode material | |
| CN108285139A (en) | A kind of preparation method and application of nitrogen-doped graphene carbon material | |
| CN104058385B (en) | A kind of method that salt recrystallization solid prepares Functional carbon material | |
| CN113277509A (en) | Porous carbon nano material and preparation method thereof | |
| CN107946557A (en) | A kind of preparation method of cobalt oxide modification Nano carbon balls electrode material | |
| CN111477891A (en) | Preparation method of nitrogen-doped porous hollow carbon sphere compound with low platinum loading capacity, product and application thereof | |
| CN103107024B (en) | A kind of nitrogenous mesoporous carbon/MnO 2composite material and preparation method thereof | |
| CN108793155A (en) | A kind of preparation method of high-specific surface area lotus root shape porous carbon materials | |
| CN108190867A (en) | A kind of method for preparing graphene | |
| CN103274385A (en) | Lithium ion battery cathode material carbon microsphere and preparation method thereof | |
| CN107265435A (en) | Preparation method of surface micropore carbon hollow ball a kind of of graphene interlayers and products thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20160601 |
|
| WD01 | Invention patent application deemed withdrawn after publication |