CN104528683B - A kind of preparation method of bamboo-like carbon nano tubes - Google Patents
A kind of preparation method of bamboo-like carbon nano tubes Download PDFInfo
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- CN104528683B CN104528683B CN201410745171.7A CN201410745171A CN104528683B CN 104528683 B CN104528683 B CN 104528683B CN 201410745171 A CN201410745171 A CN 201410745171A CN 104528683 B CN104528683 B CN 104528683B
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Abstract
The present invention relates to a kind of preparation method of bamboo-like carbon nano tubes, solve that the existing method of preparing bamboo-like carbon nano tubes exists that cost is high, environment friendly is poor, not high, the technical problem that is not easy to large-scale production of content of carbon nanotubes in product. The method comprises: 0.50-1.00g melamine is dissolved in ultra-pure water; Do you add successively 5.0-10.0mL? the dissolubility molysite of the surfactant of 0.10g/ml and 5.0-10.0mL1.0wt%, stirs, ultrasonic processing 4-6 hour; Above-mentioned solution is put into quartz boat at 80 DEG C of dried residues, and under nitrogen protection, temperature programming, to 750-900 DEG C, after heat treatment 1-3 hour, obtains bamboo-like carbon nano tubes. The method is simple and convenient, cost is low, environmental protection, is convenient to large-scale production, and the bamboo-like carbon nano tubes making has wide practical use in the field such as fuel cell, bio-sensing.
Description
Technical field
The invention belongs to nano material preparing technical field, particularly a kind of preparation of bamboo-like carbon nano tubesMethod.
Background technology
Since CNT (CNT) comes out, owing to thering are good physicochemical properties, good catalysis is livedThe advantages such as property, very active to the research of CNT. In recent years, along with the preparation method's of nano material development,People can prepare the CNT of different-shape, as Bamboo-shaped, Pacific herring herring-bone form, coniform etc. With traditional CNTDifference, Bamboo-shaped CNT is made up of shorter nodular CNT, and contain between a large amount of and be separated with the cross section causing, soIts faceted pebble carbon content is high, catalytic activity good.
But the research of preparing at present Bamboo-shaped CNT is also few, mainly contains chemical vapour deposition technique, arc dischargeMethod and pyrolysis metal organic precursor body method etc. As nano porous copper matrix is first prepared in the employings such as Liu Enzuo, then profitWith chemical vapour deposition technique can be on nano porous copper direct growth bamboo-like carbon nano tubes [Liu Enzuo, Zhang Di,Zhao Naiqin, Shi Chunsheng, Kang Jianli, He Chunnian, one direct growth Bamboo-shaped carbon on nano porous copper is receivedThe method of mitron, CN103508438A], this process is comparatively complicated, is unfavorable for large-scale production. Jin HaiyingAdopt nickel Y molecular sieve as catalyst with Wang Lijun, when heating, pass into N2/ sec-butylamine gaseous mixture, get final productTo CNT [Jin Haiying, Wang Lijun, a kind of Bamboo-shaped nitrogen-doped carbon nanometer pipe material and the system thereof of nitrogen dopingPreparation Method, CN102790224A]. As the cathod catalyst of fuel cell, there is good catalytic activity.First the employings such as Xue Bin are prepared and are used Al2O3The Cu catalyst of load adds thermal decomposition ethanol under High Purity Nitrogen atmosphereObtain bamboo-like carbon nano tubes [Xue Bin, rising sun casting moral, Liu Run, a kind of preparation of bamboo-like carbon nano tubes with high ratioMethod, CN101555009B]. Wang Xin etc. utilize the plasma chemistry gas of paraffin gas, nitrogen and oxygenDeposition is mutually prepared the directed ring of doping nitrogen in the case of the FeNi catalyst film after over etching existsShape CNT/Graphene composite metal oxide [Wang Xin, Wang Zan, Liu Jiyue, Zheng Weitao, Fan Xiaofeng, poplarOpen space, a kind of method of preparing the directed bamboo-like carbon nano tubes/Graphene composite metal oxide of doping nitrogen, CN103910349A], this product favorable orientation, productive rate are high, but in its product, contain Graphene, carbon parcel simultaneouslyMetal oxide and metal oxide nanoparticles etc. Kang Feiyu etc. are by organic at phenols ferrocene powder dissolutionIn compound, prepare reactant liquor, at high temperature inject reative cell by accurate flow pump, fully after reaction, protectingProtect cooling in atmosphere [Kang Feiyu, Lv Ruitao, Zou Lin, Gui Xuchun, the beautiful jade of looking after one's family, Wei Jinquan, Wang Kunlin, WuMoral sea, a kind of method that adopts chemical vapour deposition technique mass production of bamboo joint shaped carbon nano-tube, CN100595139C], its advantage is to produce continuously, but selected solvent cresols has larger toxicity.Chung etc. are carried on cyanamide and ferric acetate on carbon dust, under 950 DEG C of nitrogen protections, process, and acid treatment afterwards,Finally high-temperature process again, obtains the CNT/carbon nano-particle of nitrogen iron doping, has good electro-catalysisPerformance, but this material is CNT and carbon nano-particle compound, instead of the CNT of high-load[Chung,H.T.；Won,J.H.；Zelenay,P.,Activeandstablecarbonnanotube/nanoparticlecompositeelectrocatalystforoxygenreduction.NatureCommunications2013,4,1922.]. These methods or cost are high, environment friendly is poor, or in productContent of carbon nanotubes is not high, is not easy to large-scale production, has greatly limited the application of Bamboo-shaped CNT.
Summary of the invention
The present invention will solve and in prior art, prepare high, the environment of cost that the method for bamboo-like carbon nano tubes existsFriendly is poor, not high, the technical problem that is not easy to large-scale production of content of carbon nanotubes in product, provides onePlant the preparation method of bamboo-like carbon nano tubes. The method is simple and convenient, cost is low, environmental protection, is convenient to largeLarge-scale production, the bamboo-like carbon nano tubes preparing has widely in the field such as fuel cell, bio-sensingApplication prospect.
In order to solve the problems of the technologies described above, technical scheme of the present invention is specific as follows:
A preparation method for bamboo-like carbon nano tubes, comprises the following steps:
1) 0.50-1.00g melamine is dissolved in ultra-pure water;
2) add successively that the surfactant of 5.0-10.0mL0.10g/ml and 5.0-10.0mL1.0wt%'s is moltenSolution property molysite, is stirred well to evenly, more ultrasonic processing 4-6 hour;
3) by step 2) solution that obtains puts into quartz boat at 80 DEG C of dried residues, under nitrogen protectionTemperature programming is to 750-900 DEG C, and after heat treatment 1-3 hour, obtaining diameter is the Bamboo-shaped carbon of 40-110nmNanotube.
In technique scheme, described dissolubility molysite is ferric nitrate, ferric acetate or iron chloride.
In technique scheme, described surfactant is poly-(the propane diols)-block-of PEG-block-PEG (P123) orF127。
The invention has the beneficial effects as follows:
The preparation method of bamboo-like carbon nano tubes provided by the invention, material therefor is to live in melamine, surfaceProperty agent P123 orF127 and dissolubility molysite be as ferric nitrate, ferric acetate or iron chloride, only need to beHeat treatment process under nitrogen protection just can prepare bamboo-like carbon nano tubes, the method is simple and convenient,Cost is low, environmental protection, be convenient to large-scale production, the bamboo-like carbon nano tubes preparing fuel cell,The fields such as bio-sensing have wide practical use.
Brief description of the drawings
Below in conjunction with the drawings and specific embodiments, the present invention is described in further detail.
Fig. 1 is the transmission electron microscope (TEM) that adopts bamboo-like carbon nano tubes prepared by the embodiment of the present invention 1 methodFigure;
Fig. 2 is the transmission electron microscope (TEM) that adopts bamboo-like carbon nano tubes prepared by the embodiment of the present invention 2 methodsFigure;
Fig. 3 is the N that adopts bamboo-like carbon nano tubes prepared by the embodiment of the present invention 2 methods2Adsorption desorption (BET)Figure;
Fig. 4 is the Raman spectrogram that adopts bamboo-like carbon nano tubes prepared by the embodiment of the present invention 2 methodsSpectrum;
Fig. 5 is the transmission electron microscope (TEM) that adopts bamboo-like carbon nano tubes prepared by the embodiment of the present invention 3 methodsFigure.
Detailed description of the invention
Below in conjunction with accompanying drawing, the present invention is described in detail.
The preparation method of a kind of bamboo-like carbon nano tubes provided by the invention, concrete steps and condition are as follows:
1) 0.50-1.00g melamine is dissolved in ultra-pure water;
2) add successively that the surfactant of 5.0-10.0mL0.10g/ml and 5.0-10.0mL1.0wt%'s is moltenSolution property molysite, is stirred well to evenly, more ultrasonic processing 4-6 hour;
Described dissolubility molysite is ferric nitrate, ferric acetate or iron chloride;
Described surfactant be poly-(the propane diols)-block-PEG (P123) of PEG-block-orF127；
3) by step 2) solution that obtains puts into quartz boat at 80 DEG C of dried residues, under nitrogen protectionTemperature programming is to 750-900 DEG C, and after heat treatment 1-3 hour, obtaining diameter is the Bamboo-shaped carbon of 40-110nmNanotube.
Embodiment 1
1) 1.00g melamine is dissolved in 10mL ultra-pure water;
2) add successively poly-(the propane diols)-block-of PEG-block-of 5.0mL (0.10g/ml) to gather (second twoAlcohol) (P123) and the ferric nitrate of 7.5mL1.0wt%, be stirred well to evenly, more ultrasonic processing 4 hours;
3) 80 DEG C of dried residues of above-mentioned solution are put into quartz boat, under nitrogen protection, temperature programming extremely750 DEG C, heat treatment 3 hours, obtaining structure is bamboo-like carbon nano tubes. By the transmission electron microscope (TEM) of Fig. 1Figure, can clearly see the existence of bamboo-like carbon nano tubes, and its Bamboo-shaped carbon for diameter 40-110nm is receivedMitron.
Embodiment 2
1) 0.50g melamine is dissolved in 10mL ultra-pure water;
2) add successively poly-(the propane diols)-block-of PEG-block-of 7.5mL (0.10g/ml) to gather (second twoAlcohol) (P123) and the iron chloride of 5.0mL1.0wt%, be stirred well to evenly, more ultrasonic processing 5 hours;
3) 80 DEG C of dried residues of above-mentioned solution are put into quartz boat, under nitrogen protection, temperature programming extremely800 DEG C, heat treatment 1 hour, obtaining structure is bamboo-like carbon nano tubes.
The TEM figure of Fig. 2 shows, the existence of bamboo-like carbon nano tubes clearly continuously, and diameter is 40-110nmBamboo-like carbon nano tubes. We carry out N2The experiment of adsorption desorption carrys out the specific area of research material, the knot of Fig. 3Fruit shows that the specific area of material is 151.2m2/ g, and because the accumulation between CNT has also formed holeStructure, aperture is at 3.5nm. Fig. 4 is the Raman spectrogram of obtained bamboo-like carbon nano tubes, in figure 1350cm-1And 1560cm-1Two sharp-pointed Raman peaks that place exists, correspond respectively to polycrystalline graphite and disordered carbonThe G band of D band and single crystal graphite, and ID/IGBe 0.81, illustrate that the carbon nano-tube material of Bamboo-shaped is than listWall carbon nano tube has more defect sites, and this defect has important meaning for the catalytic applications that improves itJustice.
Embodiment 3
1) 1.00g melamine is dissolved in 10mL ultra-pure water;
2) add successively poly-(the propane diols)-block-of PEG-block-of 10.0mL (0.10g/ml) to gather (secondGlycol) (P123) and the ferric nitrate of 10.0mL1.0wt%, be stirred well to evenly, more ultrasonic processing 6 hours;
3) 80 DEG C of dried residues of above-mentioned solution are put into quartz boat, under nitrogen protection, temperature programming extremely900 DEG C, heat treatment 2 hours, obtaining structure is bamboo-like carbon nano tubes, its structure is as the TEM result of Fig. 5Shown in.
Embodiment 4
1) 1.00g melamine is dissolved in 10mL ultra-pure water;
2) add successively 10.0mL's (0.10g/ml)The nitric acid of F127 and 10.0mL1.0wt%Iron, is stirred well to evenly, more ultrasonic processing 6 hours;
3) 80 DEG C of dried residues of above-mentioned solution are put into quartz boat, under nitrogen protection, temperature programming extremely900 DEG C, heat treatment 1 hour, obtaining structure is bamboo-like carbon nano tubes.
Embodiment 5
1) 1.00g melamine is dissolved in 10mL ultra-pure water;
2) add successively 7.50mL's (0.10g/ml)The acetic acid of F127 and 10.0mL1.0wt%Iron, is stirred well to evenly, more ultrasonic processing 6 hours;
3) 80 DEG C of dried residues of above-mentioned solution are put into quartz boat, under nitrogen protection, temperature programming extremely750 DEG C, heat treatment 3 hours, obtaining structure is bamboo-like carbon nano tubes.
Obviously, above-described embodiment is only for example is clearly described, and not to embodimentLimit. For those of ordinary skill in the field, can also make on the basis of the above description itThe variation that it is multi-form or variation. Here without also giving exhaustive to all embodiments. And byThe apparent variation that this extends out or variation are still among the protection domain in the invention.
Claims (2)
1. a preparation method for bamboo-like carbon nano tubes, is characterized in that, comprises the following steps:
1) 0.50-1.00g melamine is dissolved in ultra-pure water;
2) add successively that the surfactant of 5.0-10.0mL0.10g/ml and 5.0-10.0mL1.0wt%'s is moltenSolution property molysite, is stirred well to evenly, more ultrasonic processing 4-6 hour;
3) by step 2) solution that obtains puts into quartz boat at 80 DEG C of dried residues, under nitrogen protectionTemperature programming is to 750-900 DEG C, and after heat treatment 1-3 hour, obtaining diameter is the Bamboo-shaped carbon of 40-110nmNanotube;
Described surfactant be poly-(the propane diols)-block-PEG (P123) of PEG-block-orF127。
2. preparation method according to claim 1, is characterized in that, described dissolubility molysite is nitric acidIron, ferric acetate or iron chloride.
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| CN104944410B (en) * | 2015-06-01 | 2017-06-16 | 北京理工大学 | A kind of method for synthesizing cobalt nanometer particle and Bamboo-shaped nitrogen-doped carbon nanometer pipe composite |
| CN105271166A (en) * | 2015-10-10 | 2016-01-27 | 浙江大学 | Method for preparation of carbon nanotube with xylitol as carbon source |
| CN106669758A (en) * | 2016-12-26 | 2017-05-17 | 华东理工大学 | Dual-function oxygen electrode catalyst containing non-noble-metal nanoparticles coated with nitrogen-doped porous carbon layer and preparation method of dual-function oxygen electrode catalyst |
| CN106629668B (en) * | 2016-12-27 | 2018-10-19 | 江汉大学 | A kind of preparation method of three-dimensional structure graphene/carbon nano-tube hydridization carbon material |
| CN106669762A (en) * | 2016-12-30 | 2017-05-17 | 华南理工大学 | Nitrogen-doped carbon nanotube/Co composite catalyst and preparation method and application thereof |
| CN106964315B (en) * | 2017-05-02 | 2019-10-11 | 安庆师范大学 | A kind of preparation method and application of hollow magnetic Co/ carbon nanotube |
| CN110170331B (en) * | 2019-06-14 | 2020-07-10 | 中国科学院长春应用化学研究所 | Iron-nitrogen double-doped hollow porous carbon sphere nano material and preparation method thereof |
| CN110690458B (en) * | 2019-08-23 | 2022-06-28 | 安徽力普拉斯电源技术有限公司 | Preparation method and application of bamboo-shaped carbon nano tube oxygen reduction electrocatalyst |
| CN112875680B (en) * | 2021-01-21 | 2022-10-14 | 电子科技大学 | Preparation method of flaky Fe-based alloy catalytic growth carbon nanotube array |
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| CN101037197A (en) * | 2007-02-14 | 2007-09-19 | 天津大学 | Method for preparing carbon nano tube including Ethylenediamine double-injection |
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| US8206624B2 (en) * | 2004-11-26 | 2012-06-26 | National Chung Cheng University | Method for producing carbon nanotube |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101037197A (en) * | 2007-02-14 | 2007-09-19 | 天津大学 | Method for preparing carbon nano tube including Ethylenediamine double-injection |
| CN101239713A (en) * | 2008-03-04 | 2008-08-13 | 江苏大学 | Method of preparing multi-wall carbon nano-tube by using polymer as raw material |
| CN102416337A (en) * | 2011-08-29 | 2012-04-18 | 重庆大学 | Method for preparing nitrogen-doped carbon nanotube fuel cell catalyst |
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