CN104528686A - Method for preparing fluorine-doped helical carbon nanotube - Google Patents
Method for preparing fluorine-doped helical carbon nanotube Download PDFInfo
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- CN104528686A CN104528686A CN201410825814.9A CN201410825814A CN104528686A CN 104528686 A CN104528686 A CN 104528686A CN 201410825814 A CN201410825814 A CN 201410825814A CN 104528686 A CN104528686 A CN 104528686A
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Abstract
The invention discloses a method for preparing a fluorine-doped helical carbon nanotube. The method comprises the following steps: at first, preparing oxide nanoparticles of nickel by utilizing the sol-gel method reduce the oxide nanoparticles of nickel with hydrogen into nickel nanoparticles to serve as a catalyst to realize high-temperature pyrolysis of acetylene and reacting the product with xenon difluoride to obtain a fluorinated helical carbon nanotube. The raw materials of the sol-gel method include nickel nitrate hexahydrate and citric acid monohydrate, and a solvent is anhydrous ethanol. According to the invention, the photoluminescence of the fluorine-doped helical carbon nanotube is increased to 263 nm and 291 nm deep UV regions, so that the shortcomings of a conventional semi-conductor material in the region are greatly avoided, and the fluorine-doped helical carbon nanotube can serve as base materials of ultraviolet fluorescence and ultraviolet detectors and is used in the fields of photoetching technique, optical information storage and pharmaceutical analysis.
Description
Technical field
The invention belongs to carbon nanotube preparation technology field, in particular to a kind of preparation method with the Fluorin doped spiral carbon nanotubes of deep UV (ultraviolet light) Photoluminescence Properties, this carbon nanotube can be used in ultra-violet light-emitting material and stores and the application of pharmaceutical analysis at photoetching technique, optical information, can also be used for the base mateiral of ultra-violet light-emitting, ultraviolet detector in addition.
Background technology
Since spiral carbon nanotubes (HCNTs) was found from 1994, with the physics and chemistry character of its excellence and wide application prospect, just cause investigators and paid close attention to greatly.It is periodically insert in the six-ring network of the carbon nanotube of straight-bar five-ring and seven-membered ring to and a kind of Helix-shaped Carbon Nanotubes of spring-like shape that forms.The spirane structure of its uniqueness determines it in optics, electricity, magnetics, microwave absorbing, mechanics and chemistry etc., all has unique character, has very large theoretical investigation and potential using value.Especially, spiral carbon nanotubes has stronger photoluminescence (PL) effect at the ultraviolet region of 368nm, and the N doping of pyrimidine Type and graphite mould effectively can strengthen its ultraviolet photoluminescence performance.But there is more dark purple outskirt photoluminescence property (emission wavelength is less than 300 nm), and then have the spiral carbon nanotubes material of the deep-UV light-emitting characteristic being less than 300nm have not been reported.
On the other hand, we notice, by fluoridize be widen carbon material can with the one of band gap extremely effective means.Such as, Graphene is a kind of can be the carbon material of zero with band gap, and after fluoridizing, its band gap can reach 3.8eV, thus is expected to have good photoluminescence property at deep UV (ultraviolet light) region (3.8eV, corresponding to ultraviolet photoluminescence wavelength ~ 327nm).Thus, we are by fluoridizing spiral carbon nanotubes, obtain there is in 263nm and 291nm deep ultraviolet region good photoluminescence performance fluoridize spiral carbon nanotubes (F-HCNT).It will have the ultraviolet laser of minimum wavelength to manufacture, and the pharmaceutical analysis with deep-UV light-emitting characteristic has a good application prospect.
Summary of the invention
Object of the present invention a kind of preparation method with the Fluorin doped spiral carbon nanotubes of deep UV (ultraviolet light) Photoluminescence Properties is provided.
Concrete steps are:
(1) 0.01mol Nickelous nitrate hexahydrate and 0.03mol monohydrate potassium are added in the Erlenmeyer flask filling 100ml dehydrated alcohol, heating in water bath to 60 DEG C also stirs, keep proceeding in beaker after 8 hours, 85 DEG C it is dried substantially after, in 175 DEG C, it is dried completely again, finally to put it in retort furnace 375 DEG C of calcinings 4 hours, obtained nickel oxide nanoparticle.
(2) nickel oxide nanoparticle taking 0.025 gram of step (1) obtained puts into tube furnace in porcelain boat; pass into hydrogen post-heating to 365 DEG C with the flow of 20ml/min and keep 1 hour obtained nano nickel particles; then hydrogen is closed; pass into acetylene with the flow of 40ml/min again and be heated to 550 ± 50 DEG C and keep 1 hour; finally close acetylene and pass into argon gas; room temperature is dropped to, obtained spiral carbon nanotubes in the protection of argon gas.
(3) spiral carbon nanotubes step (2) obtained and xenon difluoride take by the mass ratio of 1:1 ~ 10 and mix, put into polytetrafluoroethyltank tank, then airtight, again polytetrafluoroethyltank tank is put into stainless cylinder of steel, with plumbing combination pliers, the lid of stainless cylinder of steel is tightened sealing, again stainless cylinder of steel is put into retort furnace be heated to 200 ± 20 DEG C and keep 30 ~ 72 hours, after finally naturally cooling to room temperature, i.e. obtained Fluorin doped spiral carbon nanotubes.
Described raw material Nickelous nitrate hexahydrate, monohydrate potassium and dehydrated alcohol are analytical pure; Acetylene is technical pure; Argon gas and xenon difluoride are chemical pure.
The standard that the lid of described stainless cylinder of steel is tightened is after jar naturally cools to room temperature, the phenomenon that stainless cylinder of steel does not loosen or leaks gas.
Advantage of the present invention is:
(1) the inventive method production cost is lower, and be easy to processing, raw material sources are extensive.
(2) photoluminescence of Fluorin doped spiral carbon nanotubes that the inventive method obtains is promoted to 263nm and 291nm deep ultraviolet region, has greatly filled up the deficiency of existing semiconductor material in this region.
Accompanying drawing explanation
Fig. 1 is the high definition stereoscan photograph of F-HCNT-1 in embodiment 1.We can find, Fluorin doped spiral carbon nanotubes is very even, and diameter is greatly between 80 ~ 160nm, and length all more than 6 μm, and is not neat linear arrangement, but with various degree of curvature and be intertwined.
Fig. 2 is embodiment 1-4(F-HCNT-1-4) electronic spectrum (XPS).We can find, along with spiral carbon nanotubes is different from the blending ratio of xenon difluoride, the Oil repellent mixed is very different.The proportion of xenon difluoride is larger, and it is also more that corresponding fluorine mixes.
Fig. 3 is embodiment 1-4(F-HCNT-1-4) photoluminescence spectrum.We can find, although the content of fluorine changes in Fluorin doped spiral carbon nanotubes, its photoluminescence property at 263nm and 291nm deep ultraviolet can keep stable.
Embodiment
Use raw material Nickelous nitrate hexahydrate, monohydrate potassium and dehydrated alcohol for analytical pure in following examples; Acetylene is technical pure; Argon gas and xenon difluoride are chemical pure.
embodiment 1:
(1) 0.01mol Nickelous nitrate hexahydrate and 0.03mol monohydrate potassium are added in the Erlenmeyer flask filling 100ml dehydrated alcohol, heating in water bath to 60 DEG C also stirs, keep proceeding in beaker after 8 hours, 85 DEG C it is dried substantially after, in 175 DEG C, it is dried completely again, finally to put it in retort furnace 375 DEG C of calcinings 4 hours, obtained nickel oxide nanoparticle.
(2) nickel oxide nanoparticle taking 0.025 gram of step (1) obtained puts into the tube furnace that caliber is 50mm in porcelain boat; pass into the hydrogen post-heating to 365 DEG C of 20ml/min flow and keep 1 hour; then close hydrogen to pass into acetylene (flow is 40ml/min) and be heated to 550 DEG C and keep 1 hour; finally close acetylene and pass into argon gas; room temperature is dropped to, obtained spiral carbon nanotubes in the protection of argon gas.
(3) spiral carbon nanotubes step (2) obtained and xenon difluoride take by the mass ratio of 1:10 and mix, put into polytetrafluoroethyltank tank, then airtight, again polytetrafluoroethyltank tank is put into stainless cylinder of steel, sealing is tightened with plumbing combination pliers, again stainless cylinder of steel is put into retort furnace be heated to 200 DEG C and keep 30 hours, after finally naturally cooling to room temperature, i.e. obtained Fluorin doped spiral carbon nanotubes F-HCNT-1.
embodiment 2:
Change the spiral carbon nanotubes in embodiment 1 step (3) and the mixing quality ratio of xenon difluoride into 1:7, other conditions are same as embodiment 1 completely, obtained Fluorin doped spiral carbon nanotubes F-HCNT-2.
embodiment 3:
Change the spiral carbon nanotubes in embodiment 1 step (3) and the mixing quality ratio of xenon difluoride into 1:5, other conditions are same as embodiment 1 completely, obtained Fluorin doped spiral carbon nanotubes F-HCNT-3.
embodiment 4:
Change the spiral carbon nanotubes in embodiment 1 step (3) and the mixing quality ratio of xenon difluoride into 1:1, other conditions are same as embodiment 1 completely, obtained Fluorin doped spiral carbon nanotubes F-HCNT-3.
Although prior art scheme of the present invention and preferred embodiment statement as above, so itself and be not used to limit the present invention.Persond having ordinary knowledge in the technical field of the present invention, without departing from the spirit and scope of the present invention, when doing various changes, substitute and retouching.Therefore, protection scope of the present invention is when being as the criterion depending on those as defined in claim.
Claims (1)
1. a preparation method for Fluorin doped spiral carbon nanotubes, is characterized in that concrete steps are:
(1) 0.01mol Nickelous nitrate hexahydrate and 0.03mol monohydrate potassium are added in the Erlenmeyer flask filling 100ml dehydrated alcohol, heating in water bath to 60 DEG C also stirs, keep proceeding in beaker after 8 hours, 85 DEG C it is dried substantially after, in 175 DEG C, it is dried completely again, finally to put it in retort furnace 375 DEG C of calcinings 4 hours, obtained nickel oxide nanoparticle;
(2) nickel oxide nanoparticle taking 0.025 gram of step (1) obtained puts into tube furnace in porcelain boat, pass into hydrogen post-heating to 365 DEG C with the flow of 20ml/min and keep 1 hour obtained nano nickel particles, then hydrogen is closed, pass into acetylene with the flow of 40ml/min again and be heated to 550 ± 50 DEG C and keep 1 hour, finally close acetylene and pass into argon gas, room temperature is dropped to, obtained spiral carbon nanotubes in the protection of argon gas;
(3) spiral carbon nanotubes step (2) obtained and xenon difluoride take by the mass ratio of 1:1 ~ 10 and mix, put into polytetrafluoroethyltank tank, then airtight, again polytetrafluoroethyltank tank is put into stainless cylinder of steel, with plumbing combination pliers, the lid of stainless cylinder of steel is tightened sealing, again stainless cylinder of steel is put into retort furnace be heated to 200 ± 20 DEG C and keep 30 ~ 72 hours, after finally naturally cooling to room temperature, i.e. obtained Fluorin doped spiral carbon nanotubes;
Described raw material Nickelous nitrate hexahydrate, monohydrate potassium and dehydrated alcohol are analytical pure; Acetylene is technical pure; Argon gas and xenon difluoride are chemical pure;
The standard that the lid of described stainless cylinder of steel is tightened is after jar naturally cools to room temperature, the phenomenon that stainless cylinder of steel does not loosen or leaks gas.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108711519A (en) * | 2018-05-17 | 2018-10-26 | 桂林理工大学 | A kind of graphene oxide coats the preparation method of spiral carbon tube three-dimensional composite material and photoreduction N doping |
| CN110233262A (en) * | 2019-07-03 | 2019-09-13 | 桑顿新能源科技(长沙)有限公司 | O Y-oxides dopings of halogen and preparation method thereof, target, thin-film material and cathode of lithium battery, lithium battery and electrical equipment |
| CN112624089A (en) * | 2021-01-16 | 2021-04-09 | 桂林理工大学 | Method for synthesizing spiral carbon nano tube-carbon nano tube heterojunction |
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| CN101209834A (en) * | 2006-12-27 | 2008-07-02 | 北京化工大学 | Method for preparing spiral nano carbon tube rope |
| CN101284659A (en) * | 2008-01-04 | 2008-10-15 | 西北工业大学 | Carbon fluoride nanotube and method for making same |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101209834A (en) * | 2006-12-27 | 2008-07-02 | 北京化工大学 | Method for preparing spiral nano carbon tube rope |
| CN101284659A (en) * | 2008-01-04 | 2008-10-15 | 西北工业大学 | Carbon fluoride nanotube and method for making same |
Non-Patent Citations (4)
| Title |
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| E. UNGER ET AL.: "Fluorination of carbon nanotubes with xenon difluoride", 《CHEMICAL PHYSICS LETTERS》 * |
| JIANFENG WEN ET AL.: "Synthesis, Photoluminescence, and Magnetic Properties of Nitrogen-Doping Helical Carbon Nanotubes", 《THE JOURNAL OF PHYSICAL CHEMISTRY C》 * |
| WEI ZHANG ET AL.: "Comparative Study of SWCNT Fluorination by Atomic and Molecular Fluorine", 《CHEMISTRY OF MATERIALS》 * |
| 张洋等: "螺旋碳纳米管的制备、表征及性能", 《微纳电子技术》 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108711519A (en) * | 2018-05-17 | 2018-10-26 | 桂林理工大学 | A kind of graphene oxide coats the preparation method of spiral carbon tube three-dimensional composite material and photoreduction N doping |
| CN110233262A (en) * | 2019-07-03 | 2019-09-13 | 桑顿新能源科技(长沙)有限公司 | O Y-oxides dopings of halogen and preparation method thereof, target, thin-film material and cathode of lithium battery, lithium battery and electrical equipment |
| CN112624089A (en) * | 2021-01-16 | 2021-04-09 | 桂林理工大学 | Method for synthesizing spiral carbon nano tube-carbon nano tube heterojunction |
| NL2030428A (en) * | 2021-01-16 | 2022-05-16 | Univ Guilin Technology | Method for synthesizing helical carbon nanotube (hcnt)-cnt heterojunction |
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