CN105731421A - Preparation method of nitrogen-doped ultramicroporous carbon nanospheres - Google Patents
Preparation method of nitrogen-doped ultramicroporous carbon nanospheres Download PDFInfo
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- CN105731421A CN105731421A CN201610055593.0A CN201610055593A CN105731421A CN 105731421 A CN105731421 A CN 105731421A CN 201610055593 A CN201610055593 A CN 201610055593A CN 105731421 A CN105731421 A CN 105731421A
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- C01P2004/32—Spheres
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Abstract
The invention relates to a preparation method of nitrogen-doped ultramicroporous carbon nanospheres, belonging to the technical field of material preparation. The preparation method comprises the following steps: weighing 1 part by mass of phloroglucin, 0.79 part by mass of terephthalaldehyde, 445 parts by mass of water, 2.62 parts by mass of resorcinol, 0.49-4.45 parts by mass of hexamethylene tetraammonia and 1.29-3.86 parts by mass of formaldehyde; mixing the phloroglucin, terephthalaldehyde water, stirring, reacting at 70 DEG C for 1 hour, adding the resorcinol, hexamethylene tetraammonia and formaldehyde, and reacting at 35 DEG C for 24 hours, thereby obtaining a nitrogen-doped polymer solution; carrying out hydrothermal treatment on the solution at 100-110 DEG C for 24 hours, and drying the obtained product to obtain polymer nanospheres; and in a tube furnace, heating from room temperature to 700-900 DEG C at the heating rate of 2-10 DEG C/minute in a nitrogen atmosphere to perform carbonization, keeping for 4-6 hours, and naturally cooling to obtain the nitrogen-doped ultramicroporous carbon nanospheres. The nitrogen-doped ultramicroporous carbon nanospheres have the advantages of simple technique, uniform particle size and large specific area, and have important application prospects in the fields of energy storage and conversion and the like.
Description
Technical field
The preparation method that the present invention relates to a kind of N doping ultramicropore Nano carbon balls, belongs to technical field of material.
Background technology
Nano carbon balls is the Novel Carbon Nanomaterials of a kind of spherical structure, and it has the advantage such as regular shape, size tunable, suffers from being widely applied in fields such as energy storage, absorption, catalysis.Such as, " a kind of monolayer and multi-layer hollow Nano carbon balls, preparation and application thereof " (Chinese invention patent, application number: 201510137088.6), " preparation method of a kind of mesoporous trace Nano carbon balls " (Chinese invention patent, application number: 201410499699.0), " Nano carbon balls and its preparation method and application " (Chinese invention patent, application number: 201210504772.X) etc..These reports disclose the preparation method of Nano carbon balls and the application in absorption, electrode material for super capacitor etc. thereof.Therefore, Nano carbon balls causes the extensive concern of researcheres as a kind of new function material.But, the same with other material with carbon element, Nano carbon balls there is also the shortcoming of surface carbon atom relative inertness, and this makes Nano carbon balls wettability of the surface energy poor, causes that its absorption, chemical property etc. are not high.Adulterate hetero atom especially nitrogen-atoms in material with carbon element, it is possible not only to provide lone pair electrons, can also pass through to change charge density and the spin density of carbon atom, realize the surface-functionalized of material with carbon element, improve hydrophilic or the lipophile of material with carbon element, improve the wettability of material surface, expand the carbon nanomaterial range of application in fields such as catalysis, absorption, energy storage.Relevant report currently, with respect to nitrogen atom doping material with carbon element has much.Such as, " preparation of nitrogen-doped carbon composite materials and the application in ultracapacitor thereof " (Chinese invention patent, the patent No.: ZL201210475240), it was recently reported that use the compound of poly-o-phenylenediamine matrix and carbamide to prepare nitrogen-doped carbon composite materials and the application in ultracapacitor thereof." preparation method of a kind of nitrogen-doped carbon microsphere " (Chinese invention patent, application number: 201510689052.9) reports the method using ortho-aminotoluene and phosphoric acid to prepare nitrogen-doped carbon microsphere.Zhang et al. is prepared for N doping hollow Nano carbon balls (QiufengL ü by thermal depolymerization aniline/sulfonated oil composite ball, ZhiweiHe, JiayinZhang, QilangLin, Preparationandpropertiesofnitrogen-containinghollowcarbo nnanospheresbypyrolysisofpolyaniline-lignosulfonatecompo sites, JournalofAnalyticalandAppliedPyrolysis, 2011,92,152-157.).There is particle diameter relatively big (more than 100nm) or the shortcoming such as specific surface area is not high or preparation method is more complicated in Nano carbon balls prepared by these methods.
Summary of the invention
The preparation method that it is an object of the invention to openly a kind of N doping ultramicropore Nano carbon balls.The N doping ultramicropore Nano carbon balls prepared by the method has uniform particle diameter (20～40nm), the ultramicropore (0.5～0.6nm) of rule, high specific surface area (600～1400m2/ g) etc. feature.
In order to achieve the above object, phloroglucinol and terephthalaldehyde are first obtained by reacting phloroglucinol/terephthalaldehyde polymer nano-particle by the present invention, then pass through resorcinol and hexamethylene tetraammonia in polymer nano-particle surface reaction, obtaining N doping polymer nanocomposite ball, it obtains N doping ultramicropore Nano carbon balls after carbonization.The introducing of phloroglucinol/terephthalaldehyde polymer nano-particle reduces the particle diameter of N doping ultramicropore Nano carbon balls, and makes N doping ultramicropore Nano carbon balls have well-regulated ultramicropore and high-specific surface area.
Concrete preparation technology carries out as follows:
First measure phloroglucinol by mass fraction: terephthalaldehyde: water: resorcinol: hexamethylene tetraammonia: formaldehyde=1:0.79:445:2.62:0.49～4.45:1.29～3.86.Then phloroglucinol, terephthalaldehyde and water are reacted 1h in 70 DEG C under the mixing speed of 450～800 revs/min, it is thus achieved that containing the solution of phloroglucinol/terephthalaldehyde polymer nano-particle.Then, resorcinol and hexamethylene tetraammonia are joined in the solution containing phloroglucinol/terephthalaldehyde polymer nano-particle, then formaldehyde is added drop-wise in above-mentioned solution, at 35 DEG C, reacts 24h with the mixing speeds of 450～800 revs/min, obtain N doping polymer solution.Being placed in the rustless steel water heating kettle of inner liner polytetrafluoroethylene by this solution 100～110 DEG C of hydrothermal treatment consists 24h again, products therefrom dry 24～48h at 70～120 DEG C obtains polymer nanocomposite ball.Last in tube furnace, it is raised to 700～900 DEG C of carbonizations with the heating rate of 2～10 DEG C/min from room temperature under nitrogen atmosphere and keeps 4～6h, Temperature fall obtains N doping ultramicropore Nano carbon balls.
Analysis test result shows, gained N doping ultramicropore Nano carbon balls size is uniform, and diameter is 20～40nm, and specific surface area reaches 600～1400m2/ g, ultramicropore aperture is 0.5～0.6nm.During as electrode material for super capacitor, N doping ultramicropore Nano carbon balls, when electric current density is 1A/g, reaches more than 120F/g than electric capacity, and the capability retention after cycle charge-discharge 5000 times is more than 80%.
Above raw material is commercially available technical grade product.
Present invention have the advantage that
1. phloroglucinol and terephthalaldehyde are first obtained by reacting phloroglucinol/terephthalaldehyde polymer nano-particle by the present invention, then pass through resorcinol and hexamethylene tetraammonia in polymer nano-particle surface reaction, significantly reduce the particle diameter (20～40nm) of the N doping ultramicropore Nano carbon balls finally given.If not using phloroglucinol and terephthalaldehyde in course of reaction, the particle diameter of the Nano carbon balls prepared can be greatly increased (more than 100nm).
2. the present invention selects hexamethylene tetraammonia as raw material, and its hydrolysis generates formaldehyde and ammonia, act as the presoma of reaction and base catalyst.Additionally, the NH that hexamethylene tetraammonia hydrolysis generates4 +Can pass through to be reacted in polymer backbone, act as the nitrogenous source of reaction system.Therefore, the present invention has the simple advantage of preparation technology.
3. hexamethylene tetraammonia is the organic molecule with cage structure, it is possible to serve as firming agent, reduces polymer backbone contraction in carbonization process and caves in so that N doping ultramicropore Nano carbon balls has good pore structure and higher specific surface area.Analysis test result shows, the specific surface area of N doping ultramicropore Nano carbon balls is at 600～1400m2/ g, ultramicropore aperture is 0.5～0.6nm.
Detailed description of the invention
Embodiment 1
Phloroglucinol, terephthalaldehyde, water, resorcinol, hexamethylene tetraammonia and formaldehyde is measured by 1:0.79:445:2.62:0.49:1.29 mass fraction.First phloroglucinol, terephthalaldehyde and water are reacted 1h in 70 DEG C under the mixing speed of 450 revs/min, it is thus achieved that containing the solution of phloroglucinol/terephthalaldehyde polymer nano-particle.Resorcinol and hexamethylene tetraammonia are joined in the solution containing phloroglucinol/terephthalaldehyde polymer nano-particle, then formaldehyde is added drop-wise in above-mentioned solution, at 35 DEG C, react 24h with the mixing speeds of 450 revs/min, obtain N doping polymer solution.This solution is placed in 100 DEG C of hydrothermal treatment consists 24h, and products therefrom dry 48h at 70 DEG C obtains polymer nanocomposite ball.In tube furnace, being raised to 700 DEG C of carbonizations with the heating rate of 2 DEG C/min from room temperature and keep 6h under nitrogen atmosphere, Temperature fall obtains N doping ultramicropore Nano carbon balls.
Embodiment 2
Phloroglucinol, terephthalaldehyde, water, resorcinol, hexamethylene tetraammonia and formaldehyde is measured by 1:0.79:445:2.62:0.74:1.29 mass fraction.First phloroglucinol, terephthalaldehyde and water are reacted 1h in 70 DEG C under the mixing speed of 500 revs/min, it is thus achieved that containing the solution of phloroglucinol/terephthalaldehyde polymer nano-particle.Resorcinol and hexamethylene tetraammonia are joined in the solution containing phloroglucinol/terephthalaldehyde polymer nano-particle, then formaldehyde is added drop-wise in above-mentioned solution, at 35 DEG C, react 24h with the mixing speeds of 500 revs/min, obtain N doping polymer solution.This solution is placed in 100 DEG C of hydrothermal treatment consists 24h, and products therefrom dry 48h at 70 DEG C obtains polymer nanocomposite ball.In tube furnace, being raised to 850 DEG C of carbonizations with the heating rate of 5 DEG C/min from room temperature and keep 4h under nitrogen atmosphere, Temperature fall obtains N doping ultramicropore Nano carbon balls.
Embodiment 3
Phloroglucinol, terephthalaldehyde, water, resorcinol, hexamethylene tetraammonia and formaldehyde is measured by 1:0.79:445:2.62:2:3 mass fraction.First phloroglucinol, terephthalaldehyde and water are reacted 1h in 70 DEG C under the mixing speed of 700 revs/min, it is thus achieved that containing the solution of phloroglucinol/terephthalaldehyde polymer nano-particle.Resorcinol and hexamethylene tetraammonia are joined in the solution containing phloroglucinol/terephthalaldehyde polymer nano-particle, then formaldehyde is added drop-wise in above-mentioned solution, at 35 DEG C, react 24h with the mixing speeds of 700 revs/min, obtain N doping polymer solution.This solution is placed in 110 DEG C of hydrothermal treatment consists 24h, and products therefrom dry 24h at 120 DEG C obtains polymer nanocomposite ball.In tube furnace, being raised to 850 DEG C of carbonizations with the heating rate of 8 DEG C/min from room temperature and keep 4h under nitrogen atmosphere, Temperature fall obtains N doping ultramicropore Nano carbon balls.
Embodiment 4
Phloroglucinol, terephthalaldehyde, water, resorcinol, hexamethylene tetraammonia and formaldehyde is measured by 1:0.79:445:2.62:4.45:3.86 mass fraction.First phloroglucinol, terephthalaldehyde and water are reacted 1h in 70 DEG C under the mixing speed of 800 revs/min, it is thus achieved that containing the solution of phloroglucinol/terephthalaldehyde polymer nano-particle.Resorcinol and hexamethylene tetraammonia are joined in the solution containing phloroglucinol/terephthalaldehyde polymer nano-particle, then formaldehyde is added drop-wise in above-mentioned solution, at 35 DEG C, react 24h with the mixing speeds of 800 revs/min, obtain N doping polymer solution.This solution is placed in 110 DEG C of hydrothermal treatment consists 24h, and products therefrom dry 24h at 120 DEG C obtains polymer nanocomposite ball.In tube furnace, being raised to 900 DEG C of carbonizations with the heating rate of 10 DEG C/min from room temperature and keep 4h under nitrogen atmosphere, Temperature fall obtains N doping ultramicropore Nano carbon balls.
Analysis test result shows, the N doping ultramicropore Nano carbon balls size that embodiment 1-4 obtains is uniform, and diameter is 20～40nm, and specific surface area reaches 600～1400m2/ g, ultramicropore aperture is 0.5～0.6nm.The N doping ultramicropore Nano carbon balls obtained by embodiment 1-4 measures by 8:1:1 mass ratio with graphite and politef, is dissolved in ethanol solution after ground and mixed is uniform, and ultrasonic 30min forms slurry.This slurry is placed in 60 DEG C of volatilization ethanol, it is pressed into thin slice when slurry dress turns to leather hard, on thin slice, the circular electric pole piece that diameter is about about 1cm is intercepted subsequently with card punch, and it is placed on 90～100 DEG C of drying 12～24h to constant weight, use high hydraulic pressure tablet machine to urge it against the electrode of super capacitor of system on nickel screen.With N doping ultramicropore Nano carbon balls for working electrode, saturated calomel electrode is reference electrode, nickel screen electrode is to electrode, 6mol/LKOH aqueous solution is electrolyte, adopt three-electrode system, under room temperature, test specific capacity value and the cycle charge discharge electrical property of N doping ultramicropore Nano carbon balls electrode material at potential window-1.0～0V.Test result shows, as electrode material for super capacitor, N doping ultramicropore Nano carbon balls electrode, when electric current density is 1A/g, reaches more than 120F/g than electric capacity, and the capability retention after cycle charge-discharge 5000 times is more than 80%.
Above raw material is commercially available technical grade product.
Above-mentioned hydro-thermal reaction refers to: is loaded by N doping polymer solution in the rustless steel water heating kettle of inner liner polytetrafluoroethylene and carries out hydrothermal process.
Claims (1)
1. the preparation method of a N doping ultramicropore Nano carbon balls, it is characterised in that: first measure phloroglucinol by mass fraction: terephthalaldehyde: water: resorcinol: hexamethylene tetraammonia: formaldehyde=1:0.79:445:2.62:0.49～4.45:1.29～3.86；Then phloroglucinol, terephthalaldehyde and water are reacted 1h in 70 DEG C under the mixing speed of 450～800 revs/min, it is thus achieved that containing the solution of phloroglucinol/terephthalaldehyde polymer nano-particle；Then, resorcinol and hexamethylene tetraammonia are joined in the solution containing phloroglucinol/terephthalaldehyde polymer nano-particle, then, formaldehyde is added drop-wise in above-mentioned solution, at 35 DEG C, react 24h with the mixing speeds of 450～800 revs/min, obtain N doping polymer solution；It is placed in the rustless steel water heating kettle of inner liner polytetrafluoroethylene by this N doping polymer solution 100～110 DEG C of hydrothermal treatment consists 24h again, products therefrom dry 24～48h at 70～120 DEG C is obtained polymer nanocomposite ball；Finally, being placed in tube furnace by polymer nanocomposite ball, be raised to 700～900 DEG C of carbonizations with the heating rate of 2～10 DEG C/min from room temperature and keep 4～6h under nitrogen atmosphere, Temperature fall obtains N doping ultramicropore Nano carbon balls；
Above raw material is commercial reagent level product.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108283933A (en) * | 2018-02-01 | 2018-07-17 | 台州学院 | A kind of catalytic hydrogenation and dechlorination Pd-M/NOMC catalyst and its preparation method and application |
| CN112723341A (en) * | 2020-12-15 | 2021-04-30 | 南京工业大学 | Diatom doped carbon nanotube and preparation method and application thereof |
| CN116371376A (en) * | 2023-03-22 | 2023-07-04 | 中国科学院青岛生物能源与过程研究所 | Bifunctional phloroglucinol adsorption material and preparation method and application thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102976304A (en) * | 2012-11-16 | 2013-03-20 | 同济大学 | Preparation method of porous carbon nanosphere with controllable diameter |
| CN103545523A (en) * | 2013-10-30 | 2014-01-29 | 北京化工大学 | Porous carbon microsphere, preparation method and lithium ion battery negative electrode material |
| CN103864052A (en) * | 2014-03-12 | 2014-06-18 | 北京理工大学 | Hollow carbon nanosphere material and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102976304A (en) * | 2012-11-16 | 2013-03-20 | 同济大学 | Preparation method of porous carbon nanosphere with controllable diameter |
| CN103545523A (en) * | 2013-10-30 | 2014-01-29 | 北京化工大学 | Porous carbon microsphere, preparation method and lithium ion battery negative electrode material |
| CN103864052A (en) * | 2014-03-12 | 2014-06-18 | 北京理工大学 | Hollow carbon nanosphere material and preparation method thereof |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108283933A (en) * | 2018-02-01 | 2018-07-17 | 台州学院 | A kind of catalytic hydrogenation and dechlorination Pd-M/NOMC catalyst and its preparation method and application |
| CN112723341A (en) * | 2020-12-15 | 2021-04-30 | 南京工业大学 | Diatom doped carbon nanotube and preparation method and application thereof |
| CN112723341B (en) * | 2020-12-15 | 2024-02-27 | 南京工业大学 | Diatomic doped carbon nano tube and preparation method and application thereof |
| CN116371376A (en) * | 2023-03-22 | 2023-07-04 | 中国科学院青岛生物能源与过程研究所 | Bifunctional phloroglucinol adsorption material and preparation method and application thereof |
| CN116371376B (en) * | 2023-03-22 | 2024-05-24 | 中国科学院青岛生物能源与过程研究所 | Bifunctional phloroglucinol adsorption material and preparation method and application thereof |
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