CN111908451A - Preparation method of hollow vermicular carbon nano tube - Google Patents
Preparation method of hollow vermicular carbon nano tube Download PDFInfo
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- CN111908451A CN111908451A CN202010562615.9A CN202010562615A CN111908451A CN 111908451 A CN111908451 A CN 111908451A CN 202010562615 A CN202010562615 A CN 202010562615A CN 111908451 A CN111908451 A CN 111908451A
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- hollow
- vermicular carbon
- carbon nanotube
- neck flask
- vermicular
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 37
- 239000002041 carbon nanotube Substances 0.000 title claims abstract description 33
- 229910021393 carbon nanotube Inorganic materials 0.000 title claims abstract description 32
- 238000002360 preparation method Methods 0.000 title abstract description 10
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims abstract description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 15
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims abstract description 14
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 14
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000008367 deionised water Substances 0.000 claims abstract description 14
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 14
- 229920000877 Melamine resin Polymers 0.000 claims abstract description 9
- 229960000583 acetic acid Drugs 0.000 claims abstract description 9
- 239000012362 glacial acetic acid Substances 0.000 claims abstract description 9
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000008098 formaldehyde solution Substances 0.000 claims abstract description 8
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000000047 product Substances 0.000 claims abstract description 8
- 229910052786 argon Inorganic materials 0.000 claims abstract description 7
- 238000010000 carbonizing Methods 0.000 claims abstract description 7
- 229920001577 copolymer Polymers 0.000 claims abstract description 7
- 230000007935 neutral effect Effects 0.000 claims abstract description 7
- 238000001035 drying Methods 0.000 claims abstract description 6
- 238000003756 stirring Methods 0.000 claims abstract description 6
- 239000006228 supernatant Substances 0.000 claims abstract description 6
- 238000003763 carbonization Methods 0.000 claims abstract 2
- 230000035484 reaction time Effects 0.000 claims 1
- 239000000725 suspension Substances 0.000 abstract description 6
- 239000007789 gas Substances 0.000 abstract description 4
- 239000000203 mixture Substances 0.000 abstract description 2
- 239000004640 Melamine resin Substances 0.000 abstract 1
- 238000000034 method Methods 0.000 abstract 1
- 238000005406 washing Methods 0.000 abstract 1
- 229910052799 carbon Inorganic materials 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 238000001000 micrograph Methods 0.000 description 2
- 239000002086 nanomaterial Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 239000002109 single walled nanotube Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 230000002159 abnormal effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000004523 catalytic cracking Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003426 co-catalyst Substances 0.000 description 1
- ILZSSCVGGYJLOG-UHFFFAOYSA-N cobaltocene Chemical compound [Co+2].C=1C=C[CH-]C=1.C=1C=C[CH-]C=1 ILZSSCVGGYJLOG-UHFFFAOYSA-N 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- KZPXREABEBSAQM-UHFFFAOYSA-N cyclopenta-1,3-diene;nickel(2+) Chemical compound [Ni+2].C=1C=C[CH-]C=1.C=1C=C[CH-]C=1 KZPXREABEBSAQM-UHFFFAOYSA-N 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- KTWOOEGAPBSYNW-UHFFFAOYSA-N ferrocene Chemical compound [Fe+2].C=1C=C[CH-]C=1.C=1C=C[CH-]C=1 KTWOOEGAPBSYNW-UHFFFAOYSA-N 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 239000012621 metal-organic framework Substances 0.000 description 1
- 229910021404 metallic carbon Inorganic materials 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
- C01B32/158—Carbon nanotubes
- C01B32/16—Preparation
Abstract
The invention relates to a preparation method of a hollow vermicular carbon nano tube. The preparation method comprises the following steps: dispersing 6.0g of melamine and a certain amount of ZIF-67 in 100.0ml of deionized water, placing the mixture in a three-neck flask, stirring for 15 min, adding 15.0ml of formaldehyde solution into the three-neck flask after the solution is stirred uniformly, and stirring for 15 min. Dropping a certain amount of glacial acetic acid into a three-neck flask, and adding 50 percent of glacial acetic acidoAnd C, obtaining milky suspension by reaction. And (3) alternately centrifuging and washing the obtained product by using ethanol and deionized water, and drying the product in an oven after the supernatant is neutral. The obtained copolymer is protected by argon gas at 850oAnd C, carbonizing, and treating the carbonized sample with hydrofluoric acid to obtain the hollow vermicular carbon nano tube. In the invention, ZIF-67 is used as a template to synthesize melamine resin for the first time, and the hollow vermicular carbon nano tube is prepared by a simple and feasible high-temperature carbonization method.
Description
Technical Field
The invention belongs to the technical field of materials, and relates to a preparation method of a hollow vermicular carbon nanotube.
Background
The carbon nanotube is a hollow tubular structure formed by carbon elements, is also called a buckytubes, and is a one-dimensional nano material with a special structure (the diameter is between a few nanometers and a dozen nanometers, the length can reach a plurality of micrometers, and two ends of the tube are basically sealed). The material is used as a one-dimensional nano material, has light weight, perfect connection of a hexagonal structure and a plurality of abnormal mechanical, electrical and chemical properties. Cho et al at 400 for polymers obtained by polyesterification of citric acid and glycoloC heat-treated in an air atmosphere for 8 hours, and then cooled to room temperature, to obtain carbon nanotubes (Cho, w., Hamada, e., Kondo, Y.,&Takayanagi, K.Synthesis of carbon nanotubes from bulk polymer[J]applied Physics Letters, 1996,69(2), 278-279.). Sen et al 900oC under, Ar and H2And pyrolyzing ferrocene, nickelocene and cobaltocene under the atmosphere to obtain the carbon nano tube. These metal compounds, after pyrolysis, not only provide a carbon source but also catalyst particles whose growth mechanism is similar to that of catalytic cracking (Sen, r., Govindaraj, a.,& Rao, C. N. R.Carbon nanotubes by the metallocene route[J]chemical Physics Letters, 1997, 267(3-4), 276-280.). Thess et al improved the experimental conditions for the first time to obtain relatively large quantities of single-walled carbon nanotubes by laser evaporation. Experiment under 1473K, a graphite target containing Ni/Co catalyst particles is irradiated by 50 ns double-pulse laser to obtain a high-quality single-walled carbon nanotube bundle. The above work uses different reactants and preparation methods to prepare Carbon Nanotubes, but the prepared Carbon Nanotubes have low purity, are easy to tangle, require expensive lasers, and are expensive (Thessa, LeeR, NikolaevP, et al, crystaline Ropes of Metallic Carbon Nanotubes [ J]. Science, 1996,273(5274):483-487.）。
At present, the preparation of carbon nanotubes is researched more, the preparation method and the preparation process of the carbon nanotubes are different, but the preparation of the carbon nanotubes is not reported yet by taking a metal organic framework compound as a template and resin as a carbon source.
Drawings
Fig. 1 is a scanning electron microscope image of the hollow vermicular carbon nanotubes prepared in example 2 of the present invention.
Disclosure of Invention
The present invention will be further described with reference to the following embodiments and drawings, but is not limited thereto.
Meanwhile, the experimental methods described in the following examples are all conventional methods unless otherwise specified; the reagents and materials are commercially available, unless otherwise specified.
Example 1:
6.0g of melamine and 0.20 g of ZIF-67 are dissolved in 100.0ml of deionized water, placed in a three-neck flask and stirred for 15 min, and after the solution is stirred uniformly, 15.0ml of formaldehyde solution is added into the three-neck flask and stirred for 15 min. 2.00 ml of glacial acetic acid is slowly dropped into the three-neck flask and is added into the three-neck flask in 50oAnd C, reacting for 30 min to obtain milky suspension. And centrifuging the obtained product, alternately centrifuging by using ethanol and deionized water, and drying in an oven for 12h after the supernatant is neutral. The obtained copolymer is protected by argon gas at 850oAnd C, carbonizing, and treating the carbonized sample with hydrofluoric acid for 12 hours to obtain the hollow vermicular carbon nanotube.
Example 2:
6.0g of melamine and 0.40 g of ZIF-67 are dissolved in 100.0ml of deionized water, placed in a three-neck flask and stirred for 15 min, and after the solution is stirred uniformly, 15.0ml of formaldehyde solution is added into the three-neck flask and stirred for 15 min. 2.00 ml of glacial acetic acid is slowly dropped into the three-neck flask and is added into the three-neck flask in 50oAnd C, reacting for 30 min to obtain milky suspension. And centrifuging the obtained product, alternately centrifuging by using ethanol and deionized water, and drying in an oven for 12h after the supernatant is neutral. The obtained copolymer is protected by argon gas at 850oAnd C, carbonizing, and treating the carbonized sample with hydrofluoric acid for 12 hours to obtain the hollow vermicular carbon nanotube.
Fig. 1 shows a scanning electron microscope image of the hollow vermicular carbon nanotube prepared in this embodiment, and it can be seen from fig. 1 that the carbon nanotube is vermicular with different tube diameters and has an obvious structure.
Example 3:
6.0g of melamine and 0.60 g of ZIF-67 are dissolved in 100.0ml of deionized water, placed in a three-neck flask and stirred for 15 min, and after the solution is stirred uniformly, 15.0ml of formaldehyde solution is added into the three-neck flask and stirred for 15 min. 2.00 ml of glacial acetic acid is slowly dropped into the three-neck flask and is added into the three-neck flask in 50oAnd C, reacting for 30 min to obtain milky suspension. Centrifuging the obtained product, alternately centrifuging with ethanol and deionized water, and collecting supernatantAnd (5) after the solution is neutral, putting the solution into an oven to dry for 12 hours. The obtained copolymer is protected by argon gas at 850oAnd C, carbonizing, and treating the carbonized sample with hydrofluoric acid for 12 hours to obtain the hollow vermicular carbon nanotube.
Example 4:
6.0g of melamine and 0.40 g of ZIF-67 are dissolved in 100.0ml of deionized water, placed in a three-neck flask and stirred for 15 min, and after the solution is stirred uniformly, 15.0ml of formaldehyde solution is added into the three-neck flask and stirred for 15 min. 2.00 ml of glacial acetic acid is slowly dropped into the three-neck flask and is added into the three-neck flask in 50oAnd C, reacting for 30 min to obtain milky suspension. And centrifuging the obtained product, alternately centrifuging by using ethanol and deionized water, and drying in an oven for 12h after the supernatant is neutral. The obtained copolymer is put under the protection of argon and at 900 DEGoAnd C, carbonizing, and treating the carbonized sample with hydrofluoric acid for 12 hours to obtain the hollow vermicular carbon nanotube.
Example 5:
dissolving 8.0 g of melamine and 0.40 g of ZIF-67 in 100.0ml of deionized water, placing the mixture in a three-neck flask, stirring for 15 min, adding 15.0ml of formaldehyde solution into the three-neck flask after the solution is stirred uniformly, and stirring for 15 min. 2.00 ml of glacial acetic acid is slowly dropped into the three-neck flask and is added into the three-neck flask in 50oAnd C, reacting for 30 min to obtain milky suspension. And centrifuging the obtained product, alternately centrifuging by using ethanol and deionized water, and drying in an oven for 12h after the supernatant is neutral. The obtained copolymer is put under the protection of argon and at 900 DEGoAnd C, carbonizing, and treating the carbonized sample with hydrofluoric acid for 12 hours to obtain the hollow vermicular carbon nanotube.
Claims (7)
1. A hollow vermicular carbon nanotube comprising the steps of:
(1) dissolving 6.0-8.0 g of melamine and 0.20-0.60 g of ZIF-67 in 100.0ml of deionized water, and stirring for 15 min;
(2) slowly adding 15.0-30.0 ml of formaldehyde solution into the solution obtained in the step (1), and stirring for 15 min;
(3) adding 2.0-4.0 ml of glacial acetic acid into the solution obtained in the step (2) at 50%oC, reacting in a water bath for 15-60 min;
(4) centrifuging the product obtained in the step (3), alternately centrifuging by using ethanol and deionized water, and drying in an oven for 12h after the supernatant is neutral;
(5) under the protection of argon, the copolymer obtained in the step (4) is subjected to 800-900 DEG CoCarbonizing for 2 hours under C;
(6) and (4) treating the carbonized sample obtained in the step (5) with hydrofluoric acid for 12h to obtain the hollow vermicular carbon nanotube.
2. The hollow vermicular carbon nanotube as claimed in claim 1, wherein the melamine is used in the amount of 6.0g and the ZIF-67 is used in the amount of 0.40 g in the step (1).
3. The hollow vermicular carbon nanotube as claimed in claim 1, wherein the amount of the formaldehyde solution used in step (2) is 15.0 ml.
4. The hollow vermicular carbon nanotubes as claimed in claim 1, wherein the amount of glacial acetic acid used in step (3) is 2.0 ml.
5. The hollow vermicular carbon nanotube as claimed in claim 1, wherein the reaction time in step (4) is 30 min.
6. The hollow vermicular carbon nanotube as claimed in claim 1, wherein the carbonization temperature in step (5) is 850%oC。
7. A hollow vermicular carbon nanotube.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112723341A (en) * | 2020-12-15 | 2021-04-30 | 南京工业大学 | Diatom doped carbon nanotube and preparation method and application thereof |
| CN115058731A (en) * | 2022-05-11 | 2022-09-16 | 江南大学 | N, S doped porous carbon loaded Co composite material and preparation method and application thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101103150A (en) * | 2004-11-16 | 2008-01-09 | 海珀里昂催化国际有限公司 | Method for preparing single walled carbon nanotubes |
| US20120152480A1 (en) * | 2010-12-17 | 2012-06-21 | Cleveland State University | Nano-engineered ultra-conductive nanocomposite copper wire |
| CN102583324A (en) * | 2012-03-20 | 2012-07-18 | 中国地质大学（武汉） | Preparation method of amorphous state carbon nano tube |
| CN109704305A (en) * | 2019-01-22 | 2019-05-03 | 齐鲁工业大学 | It is a kind of using ZIF-67 as the preparation method and application of templated synthesis melamine resin base Carbon Materials |
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2020
- 2020-06-19 CN CN202010562615.9A patent/CN111908451A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101103150A (en) * | 2004-11-16 | 2008-01-09 | 海珀里昂催化国际有限公司 | Method for preparing single walled carbon nanotubes |
| US20120152480A1 (en) * | 2010-12-17 | 2012-06-21 | Cleveland State University | Nano-engineered ultra-conductive nanocomposite copper wire |
| CN102583324A (en) * | 2012-03-20 | 2012-07-18 | 中国地质大学（武汉） | Preparation method of amorphous state carbon nano tube |
| CN109704305A (en) * | 2019-01-22 | 2019-05-03 | 齐鲁工业大学 | It is a kind of using ZIF-67 as the preparation method and application of templated synthesis melamine resin base Carbon Materials |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN115058731A (en) * | 2022-05-11 | 2022-09-16 | 江南大学 | N, S doped porous carbon loaded Co composite material and preparation method and application thereof |
| CN115058731B (en) * | 2022-05-11 | 2024-02-13 | 江南大学 | N, S doped porous carbon loaded Co composite material and preparation method and application thereof |
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Application publication date: 20201110 |