CN104528683A - Bamboo joint-like carbon nano-tube preparation method - Google Patents
Bamboo joint-like carbon nano-tube preparation method Download PDFInfo
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- CN104528683A CN104528683A CN201410745171.7A CN201410745171A CN104528683A CN 104528683 A CN104528683 A CN 104528683A CN 201410745171 A CN201410745171 A CN 201410745171A CN 104528683 A CN104528683 A CN 104528683A
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Abstract
The present invention relates to a bamboo joint-like carbon nano-tube preparation method, wherein technical problems of high cost, poor environmental protection, not high carbon nano-tube content in the product, and inconvenient mass production of the existing bamboo joint-like carbon nano-tube preparation method are solved with the method of the present invention. The method of the present invention comprises: dissolving 0.50-1.00 g of melamine in ultrapure water, sequentially adding 5.0-10.0 mL of a 0.10 g/ml surfactant and 5.0-10.0 mL of a 1.0 wt% dissolved iron salt, uniformly stirring, carrying out an ultrasonic treatment for 4-6 h, placing the residue obtained from the solution being subjected to drying at a temperature of 80 DEG C into a quartz boat, heating to a temperature of 750-900 DEG C under nitrogen gas protection, and carrying out a heat treatment for 1-3 h to obtain the bamboo joint-like carbon nano-tubes. According to the present invention, the method has characteristics of simplicity, convenience, low cost, green environmental protection, and easy mass production, and the prepared bamboo joint-like carbon nano-tube has wide application prospects in fields of fuel cells, biological sensing, and the like.
Description
Technical field
The invention belongs to technical field of nanometer material preparation, particularly a kind of preparation method of bamboo-like carbon nano tubes.
Background technology
Since carbon nanotube (CNT) comes out, owing to having the advantage such as good physicochemical property, excellent catalytic activity, very active to the research of CNT.In recent years, along with the development of the preparation method of nano material, people can prepare the CNT of different-shape, as Bamboo-shaped, catfish bone-shaped, coniform etc.Different from traditional CNT, Bamboo-shaped CNT is made up of shorter nodular CNT, between a large amount of, be separated with the square section caused, so its faceted pebble carbon content is high, catalytic activity good.
But prepare the research of Bamboo-shaped CNT at present and seldom, mainly contain chemical Vapor deposition process, arc discharge method and pyrogenic metal organic precursor method etc.Nanoporous Copper substrate is first prepared as Liu Enzuo etc. adopts, recycling chemical Vapor deposition process can on nano porous copper direct growth bamboo-like carbon nano tubes [Liu Enzuo, Zhang Di, Zhao Naiqin, Shi Chunsheng, Kang Jianli, He Chunnian, a kind of method of direct growth bamboo-like carbon nano tubes on nano porous copper, CN 103508438 A], this process is comparatively complicated, is unfavorable for scale operation.Jin Haiying and Wang Lijun then adopts nickel Y molecular sieve as catalyzer, passes into N during heating
2/ sec-butylamine gas mixture, can obtain the carbon nanotube [Jin Haiying, Wang Lijun, a kind of Bamboo-shaped nitrogen-doped carbon nanometer pipe material and preparation method thereof, CN102790224 A] of N doping.As the cathod catalyst of fuel cell, there is good catalytic activity.Xue Bin etc. adopt first to prepare and use Al
2o
3the Cu catalyzer of load, under High Purity Nitrogen atmosphere, thermal degradation ethanol obtains bamboo-like carbon nano tubes [Xue Bin, rising sun casting moral, Liu Run, a kind of preparation method of bamboo-like carbon nano tubes with high ratio, CN 101555009 B].Wang Xin etc. utilize paraffin gas, the plasma activated chemical vapour deposition of nitrogen and oxygen, deposit at the FeNi catalyst film after over etching and prepare the directed bamboo-like carbon nano tubes/Graphene complex metal oxides [Wang Xin of doping nitrogen in case, Wang Zan, Liu Jiyue, Zheng Weitao, Fan Xiaofeng, Yang Kaiyu, a kind of method preparing the directed bamboo-like carbon nano tubes/Graphene complex metal oxides of doping nitrogen, CN103910349 A], this product favorable orientation, productive rate is high, but simultaneously containing Graphene in its product, carbon coated metal oxide compound and metal oxide nanoparticles etc.Ferrocene powder dissolution is prepared reaction solution by Kang Feiyu etc. in phenol organic compound, at high temperature enters reaction chamber by delicate flow infusion, fully in protective atmosphere, cools [Kang Feiyu after reaction; Lv Ruitao, Zou Lin, Gui Xuchun; to look after one's family beautiful jade; Wei Jinquan, Wang Kunlin, Wu Dehai; a kind of method adopting chemical Vapor deposition process mass production of bamboo joint shaped carbon nano-tube; CN100595139C], its advantage is can continuous seepage, but selected solvent cresols has larger toxicity.Cyanamide and ironic acetate are carried on carbon dust by Chung etc., process under 950 DEG C of nitrogen protections, acid treatment afterwards, last pyroprocessing again, obtain the carbon nanotube/carbon nano-particle of nitrogen Fe2O3 doping, there is good electrocatalysis characteristic, but this material is carbon nanotube and carbon nano-particle mixture, instead of carbon nanotube [Chung, the H.T. of high-content; Won, J.H.; Zelenay, P., Active and stable carbonnanotube/nanoparticle composite electrocatalyst for oxygen reduction.NatureCommunications 2013,4,1922.].These methods or cost is high, environment friendly is poor, or in product, content of carbon nanotubes is not high, is not easy to scale operation, significantly limit the application of Bamboo-shaped CNT.
Summary of the invention
The present invention will solve in prior art that the cost that the method for preparing bamboo-like carbon nano tubes exists is high, environment friendly is poor, not high, the technical problem that is not easy to scale operation of content of carbon nanotubes in product, provides a kind of preparation method of bamboo-like carbon nano tubes.The method is simple and convenient, cost is low, environmental protection, is convenient to scale operation, and the bamboo-like carbon nano tubes prepared has wide practical use in the field such as fuel cell, bio-sensing.
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 trimeric cyanamide is dissolved in ultrapure water;
2) add the tensio-active agent of 5.0-10.0mL 0.10g/ml and the solvability molysite of 5.0-10.0mL1.0wt% successively, be stirred well to evenly, then supersound process 4-6 hour;
3) by step 2) solution that obtains puts into quartz boat at 80 DEG C of dried residuums, and under nitrogen protection, temperature programming is to 750-900 DEG C, after thermal treatment 1-3 hour, namely obtains the bamboo-like carbon nano tubes that diameter is 40-110nm.
In technique scheme, described solvability molysite is iron nitrate, iron acetate or iron(ic) chloride.
In technique scheme, described tensio-active agent be poly-(propylene glycol)-block-PEG (P123) of PEG-block-or
f127.
The invention has the beneficial effects as follows:
The preparation method of bamboo-like carbon nano tubes provided by the invention, material therefor be trimeric cyanamide, tensio-active agent P123 or
f127 and solvability molysite are as iron nitrate, iron acetate or iron(ic) chloride; only need heat 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 scale operation, and the bamboo-like carbon nano tubes prepared has wide practical use in the field such as fuel cell, bio-sensing.
Accompanying drawing explanation
Below in conjunction with the drawings and specific embodiments, the present invention is described in further detail.
Fig. 1 is transmission electron microscope (TEM) figure of the bamboo-like carbon nano tubes adopting the embodiment of the present invention 1 method to prepare;
Fig. 2 is transmission electron microscope (TEM) figure of the bamboo-like carbon nano tubes adopting the embodiment of the present invention 2 method to prepare;
Fig. 3 is the N of the bamboo-like carbon nano tubes adopting the embodiment of the present invention 2 method to prepare
2adsorption desorption (BET) figure;
Fig. 4 is the Raman spectrum atlas of the bamboo-like carbon nano tubes adopting the embodiment of the present invention 2 method to prepare;
Fig. 5 is transmission electron microscope (TEM) figure of the bamboo-like carbon nano tubes adopting the embodiment of the present invention 3 method to prepare.
Embodiment
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 as follows:
1) 0.50-1.00g trimeric cyanamide is dissolved in ultrapure water;
2) add the tensio-active agent of 5.0-10.0mL 0.10g/ml and the solvability molysite of 5.0-10.0mL1.0wt% successively, be stirred well to evenly, then supersound process 4-6 hour;
Described solvability molysite is iron nitrate, iron acetate or iron(ic) chloride;
Described tensio-active agent be poly-(propylene glycol)-block-PEG (P123) of PEG-block-or
f127;
3) by step 2) solution that obtains puts into quartz boat at 80 DEG C of dried residuums, and under nitrogen protection, temperature programming is to 750-900 DEG C, after thermal treatment 1-3 hour, namely obtains the bamboo-like carbon nano tubes that diameter is 40-110nm.
Embodiment 1
1) 1.00g trimeric cyanamide is dissolved in 10mL ultrapure water;
2) iron nitrate of poly-(propylene glycol)-block-PEG (P123) and 7.5mL 1.0wt% of PEG-block-of 5.0mL (0.10g/ml) is added successively, be stirred well to evenly, then supersound process 4 hours;
3) above-mentioned solution 80 DEG C of dried residuums are put into quartz boat, temperature programming to 750 DEG C under nitrogen protection, thermal treatment 3 hours, namely obtaining structure is bamboo-like carbon nano tubes.By transmission electron microscope (TEM) figure of Fig. 1, clearly can see the existence of bamboo-like carbon nano tubes, it is the bamboo-like carbon nano tubes of diameter 40-110nm.
Embodiment 2
1) 0.50g trimeric cyanamide is dissolved in 10mL ultrapure water;
2) iron(ic) chloride of poly-(propylene glycol)-block-PEG (P123) and 5.0mL 1.0wt% of PEG-block-of 7.5mL (0.10g/ml) is added successively, be stirred well to evenly, then supersound process 5 hours;
3) above-mentioned solution 80 DEG C of dried residuums are put into quartz boat, temperature programming to 800 DEG C under nitrogen protection, thermal treatment 1 hour, namely obtaining structure is bamboo-like carbon nano tubes.
The TEM figure of Fig. 2 shows, continuously the existence of bamboo-like carbon nano tubes clearly, and diameter is the bamboo-like carbon nano tubes of 40-110nm.We carry out N
2the experiment of adsorption desorption carrys out the specific surface area of research material, and the result of Fig. 3 shows that the specific surface area of material is 151.2m
2/ g, and yet forms both pore structure due to the accumulation between carbon nanotube, aperture is at 3.5nm.Fig. 4 is the Raman spectrogram of obtained bamboo-like carbon nano tubes, 1350cm in figure
-1and 1560cm
-1two sharp-pointed Raman peaks that place exists, the G of the D band and single crystal graphite that correspond respectively to polycrystalline graphite and disordered carbon is with, and I
d/ I
gbe 0.81, illustrate that the carbon nano-tube material of Bamboo-shaped has more defect sites compared to Single Walled Carbon Nanotube, this defect is significant for the catalytic applications improving it.
Embodiment 3
1) 1.00g trimeric cyanamide is dissolved in 10mL ultrapure water;
2) iron nitrate of poly-(propylene glycol)-block-PEG (P123) and 10.0mL 1.0wt% of PEG-block-of 10.0mL (0.10g/ml) is added successively, be stirred well to evenly, then supersound process 6 hours;
3) above-mentioned solution 80 DEG C of dried residuums are put into quartz boat, temperature programming to 900 DEG C under nitrogen protection, thermal treatment 2 hours, namely obtaining structure is bamboo-like carbon nano tubes, and its structure is as shown in the TEM result of Fig. 5.
Embodiment 4
1) 1.00g trimeric cyanamide is dissolved in 10mL ultrapure water;
2) add 10.0mL's (0.10g/ml) successively
the iron nitrate of F127 and 10.0mL 1.0wt%, is stirred well to evenly, then supersound process 6 hours;
3) above-mentioned solution 80 DEG C of dried residuums are put into quartz boat, temperature programming to 900 DEG C under nitrogen protection, thermal treatment 1 hour, namely obtaining structure is bamboo-like carbon nano tubes.
Embodiment 5
1) 1.00g trimeric cyanamide is dissolved in 10mL ultrapure water;
2) add 7.50mL's (0.10g/ml) successively
the iron acetate of F127 and 10.0mL 1.0wt%, is stirred well to evenly, then supersound process 6 hours;
3) above-mentioned solution 80 DEG C of dried residuums are put into quartz boat, temperature programming to 750 DEG C under nitrogen protection, thermal treatment 3 hours, namely obtaining structure is bamboo-like carbon nano tubes.
Obviously, above-described embodiment is only for clearly example being described, and the restriction not to embodiment.For those of ordinary skill in the field, can also make other changes in different forms on the basis of the above description.Here exhaustive without the need to also giving all embodiments.And thus the apparent change of extending out or variation be still among the protection domain of the invention.
Claims (3)
1. a preparation method for bamboo-like carbon nano tubes, is characterized in that, comprises the following steps:
1) 0.50-1.00g trimeric cyanamide is dissolved in ultrapure water;
2) add the tensio-active agent of 5.0-10.0mL 0.10g/ml and the solvability molysite of 5.0-10.0mL1.0wt% successively, be stirred well to evenly, then supersound process 4-6 hour;
3) by step 2) solution that obtains puts into quartz boat at 80 DEG C of dried residuums, and under nitrogen protection, temperature programming is to 750-900 DEG C, after thermal treatment 1-3 hour, namely obtains the bamboo-like carbon nano tubes that diameter is 40-110nm.
2. preparation method according to claim 1, is characterized in that, described solvability molysite is iron nitrate, iron acetate or iron(ic) chloride.
3. preparation method according to claim 2, is characterized in that, described tensio-active agent be poly-(propylene glycol)-block-PEG (P123) of PEG-block-or
f127.
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104944410A (en) * | 2015-06-01 | 2015-09-30 | 北京理工大学 | Method for synthesis of cobalt nanoparticle and bamboo-like nitrogen doped carbon nanotube composite material |
| CN105271166A (en) * | 2015-10-10 | 2016-01-27 | 浙江大学 | Method for preparation of carbon nanotube with xylitol as carbon source |
| CN106629668A (en) * | 2016-12-27 | 2017-05-10 | 江汉大学 | Preparation method of three-dimensional-structure graphene/carbon nanotube hybrid carbon material |
| 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 |
| 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 |
| CN106964315A (en) * | 2017-05-02 | 2017-07-21 | 安庆师范大学 | A kind of preparation method and application of hollow magnetic Co/ CNTs |
| CN110170331A (en) * | 2019-06-14 | 2019-08-27 | 中国科学院长春应用化学研究所 | A kind of hollow porous carbon ball nano material of iron nitrogen codope and preparation method thereof |
| CN110690458A (en) * | 2019-08-23 | 2020-01-14 | 安徽力普拉斯电源技术有限公司 | Preparation method and application of bamboo-shaped carbon nanotube oxygen reduction electrocatalyst |
| CN112875680A (en) * | 2021-01-21 | 2021-06-01 | 电子科技大学 | Preparation method of flaky Fe-based alloy catalytic growth carbon nanotube array |
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Cited By (13)
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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 |
| CN104944410A (en) * | 2015-06-01 | 2015-09-30 | 北京理工大学 | Method for synthesis of cobalt nanoparticle and bamboo-like nitrogen doped carbon nanotube composite material |
| 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 |
| CN106629668A (en) * | 2016-12-27 | 2017-05-10 | 江汉大学 | Preparation method of three-dimensional-structure graphene/carbon nanotube hybrid 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 |
| CN106964315A (en) * | 2017-05-02 | 2017-07-21 | 安庆师范大学 | A kind of preparation method and application of hollow magnetic Co/ CNTs |
| 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 |
| CN110170331A (en) * | 2019-06-14 | 2019-08-27 | 中国科学院长春应用化学研究所 | A kind of hollow porous carbon ball nano material of iron nitrogen codope and preparation method thereof |
| 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 |
| CN110690458A (en) * | 2019-08-23 | 2020-01-14 | 安徽力普拉斯电源技术有限公司 | Preparation method and application of bamboo-shaped carbon nanotube oxygen reduction electrocatalyst |
| CN112875680A (en) * | 2021-01-21 | 2021-06-01 | 电子科技大学 | Preparation method of flaky Fe-based alloy catalytic growth carbon nanotube array |
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