CN112978715A - Carbon nano tube using alcohol solvent as carbon source and preparation method thereof - Google Patents
Carbon nano tube using alcohol solvent as carbon source and preparation method thereof Download PDFInfo
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Abstract
The invention relates to a carbon nano tube using an alcohol solvent as a carbon source and a preparation method thereof. Dissolving metal salt and urea in an alcohol solvent, carrying out reflux reaction, and obtaining a Metal Organic Framework (MOF) material after the reaction is completed; then, under the inert gas atmosphere, alcohol solvent is used as a carbon source, and the carbon nanotube is obtained by calcining at the temperature of 700-900 ℃. By this extension, a functionalized carbon nanotube can be obtained by a one-step process using a functional solvent and an alcohol containing a heteroatom such as fluorine as a carbon source.
Description
Technical Field
The invention relates to the technical field of carbon nanotubes, in particular to a carbon nanotube taking an alcohol solvent as a carbon source and a preparation method thereof.
Background
The carbon nano tube has high length-diameter ratio, Young modulus and high conductivity, so the carbon nano tube plays a significant role in the fields of composite material preparation, supercapacitors, photocatalysis, microelectronics, nano-electronics and the like. As early as 1953, CO and Fe were carried out at 450 ℃ in some cases3O4A linear carbon structure material similar to carbon nanotubes was found in the reaction. Several decades later, the electron microscopy of basic research laboratory of NEC, Iijima, in 1991, has surprisingly discovered the synthesis of fullerenes (C60) by high-resolution transmission microscopy (HRTEM) in a study using graphite arc dischargeThe novel coaxial tubular fullerene carbon with a complete molecular structure, namely CNTs, is formed by the layered graphite shells. The material has a hollow structure with the size of nanometer magnitude, and due to the excellent physical and chemical properties, researches on the enthusiasm of carbon nanometer materials by scientific researchers are promoted.
At present, common techniques for preparing carbon nanotubes include: arc discharge, laser evaporation, flame, and Chemical Vapor Deposition (CVD). Compared with the first three methods, the chemical vapor deposition method has the potential of producing high-quality carbon nanotubes in a large scale. The traditional chemical vapor deposition method is to introduce hydrocarbons or carbon-containing oxides into a high-temperature tubular furnace containing a catalyst, and form carbon nanotubes after metal catalytic decomposition. The method has high yield, and particularly, the morphology and the structure of the carbon nano tube can be controlled by adjusting the catalyst and the synthesis conditions. However, the following disadvantages still exist at present: firstly, the used metal catalyst has catalytic activity only through multi-step pretreatment; secondly, the gaseous hydrocarbon substances or gaseous carbon oxides as carbon sources have certain limitations in actual operation, storage and transportation; thirdly, the prepared carbon nano tube product still has the conditions of low proportion of tubular structures, non-uniform tube diameters, more crystallization defects and the like, so that the carbon nano tube has the defects of low graphitization degree, easy bending and deformation of the carbon nano tube and the like. The above reasons have resulted in limitations in the industrial application of chemical vapor deposition processes.
Many researchers have proposed many new strategies to solve the above problems in recent years. Kenji Hata et al showed that the presence of Water can optimize the morphology and increase the purity of Carbon nanotubes (Water-Assisted high efficiency Synthesis of Impurity-Free Single-Walled Carbon nanotubes. science,2004,306: 1362-. 1364.). The research takes ethylene as a carbon source, adds a certain amount of water, and successfully prepares the high-quality single-walled carbon nanotube under the action of different catalysts through a chemical vapor deposition method. This demonstrates that the addition of a small amount of water during calcination removes amorphous carbon, improves catalyst activity and life, and also helps to solve the aforementioned problems encountered during carbon nanotube growth. Therefore, the water-assisted carbon nanotube growth method is applicableThe method can be used for producing the carbon nano tubes in a large scale, and simultaneously can solve key problems such as expansibility, purity, cost and the like, thereby providing a new direction for a carbon nano tube synthesis method. With the widespread use of carbon nanotubes as catalyst materials and the further demand of people for higher performance sources, there is a trend to develop better quality carbon nanotube catalysts, and the quality of carbon nanotubes is improved mainly by doping with heteroatoms at the present stage. For example, Hou et al use polypyrrole as a nitrogen source, acetylene as a carbon source, Fe3O4Is an iron source, and adopts an autocatalytic CVD method to prepare Fe under the condition of low-temperature annealing3The experimental results and theoretical calculation prove that the synergistic effect of heteroatom doping can improve the lithium storage performance of the carbon nano-tube (A factor self-catalyzed CVD method to synthesis Fe)3C/N-doped carbon nanofibers as lithium storage anode with improved rate capability and cyclability.Journal of Materials Science&Technology,2020,44: 229-. Nowadays, how to simply dope heteroatom into carbon nanotube and reduce its production cost to realize industrial scale production of carbon nanotube has become another focus of attention.
Disclosure of Invention
In order to solve the above technical problems, the present invention aims to provide a carbon nanotube using an alcohol solvent as a carbon source and a preparation method thereof. The method adopts the self-made MOF material as a catalyst, uses a liquid alcohol solvent as a carbon source, and calcines the catalyst to obtain the carbon nano-tubes, and in addition, the method also expands the application of a functionalized solvent as a carbon source to realize the batch production of the functionalized carbon nano-tubes.
One of the purposes of the invention is to provide a method for preparing carbon nanotubes by using an alcohol solvent as a carbon source, which comprises the following steps:
(1) dissolving metal salt and urea in an alcohol solvent, carrying out reflux reaction on the obtained mixed solution at 50-80 ℃, and obtaining an MOF material after complete reaction;
(2) and calcining the MOF material serving as a catalyst and an alcohol solvent serving as a carbon source at the temperature of 700-900 ℃ to obtain the carbon nano tube.
Further, in the step (1), the molar ratio of the total moles of the metal salt to the urea is 1: 5-8.
Further, in the step (1), the gold is selected from at least two of cobalt, nickel, manganese, cadmium, iron, copper, zinc, chromium, lead acetate.
Further, in the step (1), the alcohol solvent is one of methanol, ethanol, propanol or isopropanol.
Further, in the step (2), the alcohol solvent is one or more of methanol, ethanol, propanol, octafluoropentanol, trifluoroethanol, tetrafluoropropanol, monoethanolamine, diethanolamine, and triethanolamine.
Further, in the step (2), before the calcination at the temperature of 700-900 ℃, the step of calcination at the temperature of 150-200 ℃ is also included for 0.5-1.5 h.
Further, in step (2), calcining is carried out at the temperature of 700-900 ℃ for 2-4 h.
Further, in the step (2), the protective atmosphere is an inert gas.
The invention takes self-made MOF material catalyst and liquid alcohol as solvent and carbon source, fully disperses the catalyst in the solvent by ultrasound, and calcines the catalyst under high temperature condition to generate carbon nano tube. The MOF material synthesized in the step (1) of the invention is used as a catalyst for the growth of carbon nanotubes, and the components, the shape and the size of the MOF material play a decisive role in the growth of the carbon nanotubes. In addition, liquid alcohol is used as a carbon source, compared with a gas carbon source, the liquid carbon source has the advantages of wide source, low price, convenient transportation, low carbon nanotube synthesis cost, low device construction requirement and better controllability during calcination. Finally, under the condition of high temperature, the cracking reduction of the metal catalyst and the growth of the carbon nano tube occur simultaneously, and the carbon nano tube is formed in situ.
The invention also aims to provide the functionalized carbon nanotube prepared by the preparation method, which comprises the heteroatom-doped carbon nanotube.
Further, the heteroatoms are selected from nitrogen or/and fluorine.
By the scheme, the invention at least has the following advantages:
the invention provides a simple controllable synthetic carbon nano tube and a preparation method thereof. And dissolving the self-made MOF material in an alcohol solvent atmosphere, and calcining to obtain a carbon nano tube product. The method is simple and convenient to operate, and the carbon nano tube obtained by calcining the carbon nano tube by using the alcohol solvent as the carbon source is uniform in size.
The method has certain universality, can be suitable for catalyst systems of MOF materials containing different metal salts, and obtains the carbon nano tube by calcining. The invention has simple and convenient calcining process and strong operability, and is suitable for industrialized mass production. The functionalized carbon nano tube can be obtained by a one-step method by using the functional solvent and alcohol containing heteroatoms such as fluorine as a carbon source.
The foregoing description is only an overview of the technical solutions of the present invention, and in order to make the technical solutions of the present invention more clearly understood and to implement them in accordance with the contents of the description, the following is a preferred embodiment of the present invention and is described with reference to the detailed drawings.
Drawings
FIG. 1 is a TEM image of the calcined product in different solvents;
FIG. 2 is a photograph showing a physical example of a calcined product obtained by adding ethanol and not adding ethanol;
FIG. 3 is a TEM image of the calcined product obtained with and without the addition of ethanol;
FIG. 4 is a TEM image of the calcined product in example 3;
FIG. 5 is a photograph comparing before and after calcination of CoNi-U;
FIG. 6 is SEM and TEM images of CoNi-CNTs-1 and CoNi-CNTs-2;
FIG. 7 is an SEM, TEM image, HR-TEM and elemental distribution plot of CoNiMn-CNTs;
FIG. 8 is a XRD contrast of CoNi-CNTs-1, CoNi-CNTs-2 and CoNiMn-CNTs;
FIG. 9 is an SEM, TEM image, HR-TEM image of CoCdFe-CNTs and an element distribution diagram thereof.
Detailed Description
The following examples are given to further illustrate the embodiments of the present invention. The following examples are intended to illustrate the invention but are not intended to limit the scope of the invention.
Example 1
To demonstrate that ethanol has an optimizing effect on carbon nanotube growth, the following experiments were performed to verify that:
(1) mixing of Co (OAc)2·4H2O (1.0mmol) and urea (5.0mmol) were dissolved in 50mL of ethanol and reacted at 50 ℃ under reflux for 8 h. After cooling, centrifugally collecting the product, and vacuum-drying at 70 ℃ for 12h to obtain the MOF material Co-U-1.
(2) Two portions of Co-U-1(50mg) are respectively put into a centrifuge tube, 3mL of normal hexane and 3mL of ethanol are respectively added, and the mixture is calcined under the same condition after being subjected to ultrasonic treatment for 30 min. Calcining conditions are as follows: in the nitrogen atmosphere, the temperature rise rate of the first stage of calcination is 2 ℃ min-1Keeping the temperature at 150 ℃ for 1.5 h; then the second stage of calcination, the heating rate is 2 ℃ for min-1The heat preservation temperature is 700 ℃, and the heat preservation time is 4 hours.
As shown in fig. 1, by comparison of TEM, it was found that: the carbon nanotubes obtained by calcining in n-hexane containing no alcoholic hydroxyl group (fig. 1a) have a rougher wall surface and more impurities than the carbon nanotubes obtained by calcining in ethanol (fig. 1 b); the carbon nano tube generated in the ethanol has smooth tube wall surface and less impurities. The C-O bond of the ethanol solvent is broken to generate water under the high-temperature condition, the water is favorable for preventing carbon and metal particles from agglomerating, the activity of more metal catalysts is ensured, and simultaneously, a carbon source can be fully diffused on the surfaces of the catalysts, so that the effect of further promoting the water to act as a protective agent is achieved, the amorphous carbon nano tube is reduced, and the purer carbon nano tube can be obtained.
Example 2
In order to verify whether ethanol can have certain influence on the growth of the carbon nanotubes, the following experiments are carried out for verification:
(1) mixing of Co (OAc)2·4H2O (1.0mmol) and urea (7.0mmol) were dissolved in 60mL of ethanol and reacted at 60 ℃ under reflux for 7 h. After cooling, the product is collected by centrifugation and dried for 12h in vacuum at 70 ℃ to obtain the MOF material Co-U-2.
(2) Two portions of Co-U-2(100mg) are respectively put into a centrifuge tube, 5mL of ethanol is added into one portion, ultrasonic treatment is carried out for 30min, and no ethanol is added into the other portion. Two samples were identicalCalcining under the condition. Calcining conditions are as follows: in the nitrogen atmosphere, the temperature rise rate of the first stage of calcination is 2 ℃ min-1Keeping the temperature at 160 ℃ for 1 h; then the second stage of calcination, the heating rate is 2 ℃ for min-1The heat preservation temperature is 800 ℃, and the heat preservation time is 3 hours.
As shown in fig. 2 (physical photograph), the calcined products were significantly different between the samples with and without ethanol. By weight comparison, the net weight of the sample calcined with ethanol is 150mg, and the net weight of the sample calcined without ethanol is 80mg, and the yield of the calcined product in the presence of ethanol is higher. Considering that the calcination is carried out in an inert atmosphere (N)2) The method is carried out without participating in the growth of the carbon nano tube, no external carbon source is provided, and the yield of the carbon nano tube has obvious difference compared with the method without ethanol calcination, so that the ethanol can be used as a solvent medium to uniformly disperse the catalyst and the metal salt and can also be used as a carbon source for the growth of the carbon nano tube. Further, it was observed by TEM that the carbon nanotubes were produced by calcination after ethanol addition (fig. 3a), whereas the product directly calcined without ethanol addition was mostly massive agglomerates (fig. 3 b). It can be stated that ethanol as a solvent is also a critical factor in regulating the growth of carbon nanotubes.
Example 3
To obtain functionalized carbon nanotubes, it was further demonstrated that the solvent participates in the growth of carbon nanotubes as a carbon source, and we exchanged the solvent added by calcination for octafluoropentanol. The experimental procedure was as follows:
(1) mixing of Co (OAc)2·4H2O (1.0mmol) and urea (8.0mmol) were dissolved in 60mL of ethanol and reacted at 70 ℃ under reflux for 5 hours. After cooling, centrifugally collecting the product, and vacuum-drying at 70 ℃ for 12h to obtain the MOF material Co-U-3.
(2) Co-U-3(150mg) was put into a centrifuge tube, sonicated in 4mL of octafluoropentanol and 4mL of ethanol for 30min, and calcined. Calcining conditions are as follows: in the nitrogen atmosphere, the temperature rise rate of the first stage of calcination is 2 ℃ min-1Keeping the temperature at 180 ℃ for 0.5 h; then the second stage of calcination, the heating rate is 2 ℃ for min-1The heat preservation temperature is 900 ℃, and the heat preservation time is 2 hours.
As shown in the TEM characterization chart of fig. 4, the octafluoropentanol solvent is used, the calcination conditions are unchanged, the carbon nanotubes can still be obtained, and the surface of the tube wall is smooth, further proving that the alcohol solvent can adjust the surface roughness of the carbon nanotubes, the diameter size of the carbon nanotubes is about 50nm, and the thickness of the tube wall is about 15 nm. Meanwhile, EDS element analysis finds that fluorine exists, and proves that the method is applicable to a functionalized carbon source solvent and can be used for synthesizing functionalized carbon nanotubes (Table 1).
Table 1: EDS diagram of the product
| Element(s) | wt％ | At％ |
| CK | 59.08 | 69.49 |
| Co K | 7.58 | 3.33 |
| NK | 9.34 | 8.75 |
| OK | 14.27 | 11.71 |
| FK | 9.73 | 6.72 |
| Total amount of | 100.00 | 100.00 |
Example 4
(1) Mixing of Co (OAc)2·4H2O(0.5mmol)、Ni(OAc)2·4H2O (0.5mmol) and urea (8mmol) were dissolved in 70mL of ethanol and reacted at 80 ℃ under reflux for 4 h. After cooling, the product is collected by centrifugation and dried in vacuum at 70 ℃ for 12h, and the MOF material CoNi-U-1 is obtained.
(2) CoNi-U-1(500mg) is taken and placed in a centrifuge tube, 15mL of absolute ethyl alcohol is added, and after 30min of ultrasonic treatment, calcination is carried out. The calcination conditions were as follows: in the nitrogen atmosphere, the temperature rise rate of the first stage of calcination is 2 ℃ min-1Keeping the temperature at 200 ℃ for 0.5 h; then the second stage of calcination, the heating rate is 2 ℃ for min-1The heat preservation temperature is 700 ℃, and the heat preservation time is 4 hours. And finally obtaining a product CoNi-CNTs-1.
Example 5
(1) Mixing of Co (OAc)2·4H2O(0.2mmol)、Ni(OAc)2·4H2O (0.8mmol) and urea (5mmol) were dissolved in 50mL of ethanol and reacted at 80 ℃ under reflux for 4 h. After cooling, the product is collected by centrifugation and dried in vacuum at 70 ℃ for 12h, and the MOF material CoNi-U-2 is obtained.
(2) CoNi-U (125mg) is taken and placed in a centrifuge tube, 5mL of absolute ethyl alcohol is added, and after 30min of ultrasonic treatment, calcination is carried out. The calcination conditions were as follows: in the nitrogen atmosphere, the temperature rise rate of the first stage of calcination is 2 ℃ min-1Keeping the temperature at 180 ℃ for 1 h; then the second stage of calcination, the heating rate is 2 ℃ for min-1The heat preservation temperature is 800 ℃, and the heat preservation time is 3 hours. And finally obtaining a product CoNi-CNTs-2.
FIGS. 5a and 5b are pictorial representations of CoNi-U before and after calcination. It can be seen that the solution in the porcelain ark changed from brown to fluffy black after calcination, and SEM and TEM characterization also found further carbon nanotubes. By contrast, the mass of the sample before calcination (without ethanol) is 750mg, and the mass of the sample after calcination is 1500mg, so that the weight of the sample is increased, which further proves that the ethanol solvent can be used as a basis for carbon source, and also shows that the method has the potential of mass production of carbon nanotubes and can be used for industrial production.
FIGS. 6a and 6c are SEM and TEM images of CoNi-CNTs-1, respectively; FIGS. 6b and 6d are SEM and TEM images of CoNi-CNTs-2, respectively. The carbon nanotubes are typically fibrous as seen in the SEM image. Further, it can be seen from the TEM image that the carbon nanotube has obvious hollow channels, and the end of the carbon nanotube is wrapped with granular material; the diameter of the carbon nano tube in the CoNi-CNTs-1 is about 30nm, and the thickness of the tube wall is about 10 nm; the diameter of the carbon nano tube in the CoNi-CNTs-2 is about 40nm, and the thickness of the tube wall is about 10 nm.
Example 6
(1) Mixing of Co (OAc)2·4H2O(0.3mmol)、Ni(OAc)2·4H2O(0.3mmol)、Mn(OAc)2·4H2O (0.4mmol) and urea (7mmol) were dissolved in 70mL of ethanol and reacted at 70 ℃ under reflux for 5 h. After cooling, centrifugally collecting the product, and vacuum-drying at 70 ℃ for 12h to obtain the MOF material CoNiMn-U.
(2) CoNiMn-U (175mg) is taken and put into a centrifuge tube, 6mL of absolute ethyl alcohol is added, and after 30min of ultrasonic treatment, calcination is carried out. The calcination conditions were as follows: in the nitrogen atmosphere, the temperature rise rate of the first stage of calcination is 2 ℃ min-1Keeping the temperature at 160 ℃ for 1.5 h; then the second stage of calcination, the heating rate is 2 ℃ for min-1The heat preservation temperature is 700 ℃, and the heat preservation time is 3.5 h. And finally obtaining a product CoNiMn-CNTs.
FIGS. 7a and 7b are SEM and TEM images of CoNiMn-CNTs, respectively, FIG. 7C1 is HR-TEM image of CoNiMn-CNTs, and FIGS. 7C2-C7 are distribution diagrams of Co, Ni, Mn, C, N, O elements in sequence. Through SEM and TEM images, the structure of CoNiMn-CNTs similar to CoNi-CNTs-1 and CoNi-CNTs-2 can be seen, the diameter of the carbon nano tube is about 30nm, and the thickness of the tube wall is about 10 nm. Meanwhile, the elemental analysis chart shows that the metal elements Co, Ni and Mn used as the catalyst are mainly distributed at the end of the carbon nano tube in a granular manner. It can also be seen that O is also distributed mainly at the ends of the carbon nanotubes, and C and N are distributed mainly in the walls of the carbon nanotubes.
FIG. 8 is a XRD contrast plot of CoNi-CNTs-1, CoNi-CNTs-2 and CoNiMn-CNTs, wherein the metals Co and Ni exist mainly in the form of metal simple substance in CoNi-CNTs-1 and CoNi-CNTs-2, the metals Co and Ni also exist mainly in the form of metal simple substance in CoNiMn-CNTs, and Mn exists mainly in the form of MnO.
Example 7
(1) Mixing of Co (OAc)2·4H2O(0.3mmol)、Cd(OAc)2·4H2O(0.3mmol)、Fe(OAc)2·4H2O (0.3mmol) and urea (8mmol) were dissolved in 50mL of ethanol and reacted at 80 ℃ under reflux for 5 h. After cooling, centrifugally collecting the product, and vacuum-drying at 70 ℃ for 12h to obtain the MOF material CoCdFe-U.
(2) CoCdFe-U (150mg) is taken and put into a centrifuge tube, 3mL of absolute ethyl alcohol is added, and after 30min of ultrasonic treatment, calcination is carried out. The calcination conditions were as follows: in the nitrogen atmosphere, the temperature rise rate of the first stage of calcination is 2 ℃ min-1Keeping the temperature at 200 ℃ for 0.5 h; then the second stage of calcination, the heating rate is 2 ℃ for min-1The heat preservation temperature is 800 ℃, and the heat preservation time is 3 hours. Finally obtaining the product CoCdFe-CNTs.
FIGS. 9a and 9b are SEM and TEM images of CoCdFe-CNTs, respectively, FIG. 9C1 is HR-TEM image of CoCdFe-CNTs, and FIGS. 9C2-C7 are distribution diagrams of Co, Cd, Fe, C, N, O elements in sequence. According to SEM and TEM images, the structure of CoCdFe-CNTs similar to CoNiMn-CNTs can be seen, the diameter of the carbon nano tube is about 100nm, and the thickness of the tube wall is about 20 nm. Meanwhile, the element analysis chart shows that the metal elements Co, Cd and Fe used as the catalyst are mainly distributed at the end of the carbon nano tube in a granular manner. It can also be seen that O is also distributed mainly at the ends of the carbon nanotubes, and C and N are distributed mainly in the walls of the carbon nanotubes.
The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, it should be noted that, for those skilled in the art, many modifications and variations can be made without departing from the technical principle of the present invention, and these modifications and variations should also be regarded as the protection scope of the present invention.
Claims (9)
1. A carbon nanotube using alcohol solvent as carbon source and its preparation method, characterized by comprising the following steps:
(1) dissolving metal salt and urea in an alcohol solvent, carrying out reflux reaction on the obtained mixed solution at 50-80 ℃, and obtaining an MOF material after complete reaction;
(2) and calcining the MOF material at the temperature of 700-900 ℃ in the alcohol solvent atmosphere to obtain the carbon nano tube.
2. The method of claim 1, wherein: in the step (1), the molar ratio of the total moles of the metal salt to the urea is 1: 5-8.
3. The method of claim 1, wherein: in the step (1), the metal salt is selected from one or more of cobalt, nickel, manganese, cadmium, iron, copper, zinc, chromium and lead acetate.
4. The method of claim 1, wherein: in the step (1), the alcohol solvent is one of methanol, ethanol, propanol or isopropanol.
5. The method of claim 1, wherein: in the step (2), the alcohol solvent is one or more of methanol, ethanol, propanol, octafluoropentanol, trifluoroethanol, tetrafluoropropanol, monoethanolamine, diethanolamine and triethanolamine.
6. The method of claim 1, wherein: in the step (2), a step of calcining at the temperature of 150-200 ℃ for 0.5-1.5h is further included before calcining at the temperature of 700-900 ℃.
7. The method of claim 1, wherein: in the step (2), calcining is carried out for 2-5h at the temperature of 700-900 ℃.
8. A carbon nanotube produced by the production method according to any one of claims 1 to 6.
9. The carbon nanotube of claim 8, wherein: the carbon nano tube is doped with heteroatoms, and the heteroatoms are selected from nitrogen or/and fluorine.
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|---|---|---|---|---|
| CN115520854A (en) * | 2022-10-13 | 2022-12-27 | 潍坊科技学院 | Method for preparing carbon nano tube by using recovered ternary lithium battery positive electrode leaching solution |
| CN115872391A (en) * | 2022-12-21 | 2023-03-31 | 上海懿禾嘉朋新材料科技有限公司 | Single-walled carbon nanotube prepared by metal organic framework and preparation method and application thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106276847A (en) * | 2016-07-20 | 2017-01-04 | 苏州顾氏新材料有限公司 | A kind of preparation method of CNT |
| CN109354137A (en) * | 2018-11-27 | 2019-02-19 | 浙江工业大学 | The preparation and application of the derivative porous carbon composite electrode material of carbon nanotube/MOF |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103816905B (en) * | 2014-03-21 | 2016-03-30 | 南开大学 | A kind of preparation method of carbon nanotube loaded nanometer cobalt catalyst |
| GB201410214D0 (en) * | 2014-06-09 | 2014-07-23 | Univ Surrey | A method for graphene and carbon nanotube growth |
| CN109873158B (en) * | 2017-12-01 | 2021-07-09 | 中国科学院大连化学物理研究所 | Carbon material for lithium-sulfur battery and preparation and application thereof |
| CN110787819B (en) * | 2019-08-19 | 2022-10-28 | 浙江工业大学 | Cobalt diselenide/nitrogen-doped carbon nano material composite electrode catalytic material, and preparation method and application thereof |
-
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106276847A (en) * | 2016-07-20 | 2017-01-04 | 苏州顾氏新材料有限公司 | A kind of preparation method of CNT |
| CN109354137A (en) * | 2018-11-27 | 2019-02-19 | 浙江工业大学 | The preparation and application of the derivative porous carbon composite electrode material of carbon nanotube/MOF |
Cited By (3)
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| CN115520854A (en) * | 2022-10-13 | 2022-12-27 | 潍坊科技学院 | Method for preparing carbon nano tube by using recovered ternary lithium battery positive electrode leaching solution |
| CN115872391A (en) * | 2022-12-21 | 2023-03-31 | 上海懿禾嘉朋新材料科技有限公司 | Single-walled carbon nanotube prepared by metal organic framework and preparation method and application thereof |
| CN115872391B (en) * | 2022-12-21 | 2023-11-21 | 上海懿禾嘉朋新材料科技有限公司 | Single-walled carbon nanotube prepared by metal organic framework, and preparation method and application thereof |
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