CN111392713A - Transition metal modified carbon nanotube material and preparation method thereof - Google Patents
Transition metal modified carbon nanotube material and preparation method thereof Download PDFInfo
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- CN111392713A CN111392713A CN202010238161.XA CN202010238161A CN111392713A CN 111392713 A CN111392713 A CN 111392713A CN 202010238161 A CN202010238161 A CN 202010238161A CN 111392713 A CN111392713 A CN 111392713A
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- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
- C01B32/158—Carbon nanotubes
- C01B32/16—Preparation
- C01B32/162—Preparation characterised by catalysts
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- C—CHEMISTRY; METALLURGY
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- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2202/00—Structure or properties of carbon nanotubes
- C01B2202/06—Multi-walled nanotubes
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2202/00—Structure or properties of carbon nanotubes
- C01B2202/20—Nanotubes characterized by their properties
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- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2202/00—Structure or properties of carbon nanotubes
- C01B2202/20—Nanotubes characterized by their properties
- C01B2202/36—Diameter
Abstract
The invention belongs to the field of nano materials, and particularly relates to a transition metal modified carbon nano tube material and a preparation method thereof. The method comprises the following steps: weighing Fe (NO)3)3·9H2O、Co(NO3)2·6H2O or Ni (NO)3)2·6H2And O, adding cyanamide, performing ultrasonic treatment to obtain a precursor, placing the ark filled with the precursor in a vacuum drying box for drying, finally placing the ark in a tube furnace, calcining under the protection of nitrogen, and naturally cooling to obtain the transition metal modified carbon nanotube. Compared with the traditional chemical vapor deposition, the preparation method of the transition metal modified carbon nanotube material does not need harsh reaction conditions and expensive equipment, has simple and efficient preparation process, easily obtained raw materials and low production cost, and can realize large-scale production; the obtained transition metal iron, cobalt and nickel modified carbon nano tube has excellent performance and wide application prospect.
Description
[ technical field ] A method for producing a semiconductor device
The invention relates to the field of nano materials, in particular to a transition metal modified carbon nano tube material and a preparation method thereof.
[ background of the invention ]
At present, the traditional methods for preparing carbon nanotubes include arc discharge, chemical vapor deposition, laser evaporation and the like.
The arc discharge method needs to introduce inert gas or hydrogen into a vacuum reaction chamber, respectively adopts a graphite rod as a cathode and an anode, and obtains a carbon nano tube product at the cathode through arc discharge.
The chemical vapor deposition method produces carbon nanotubes by decomposition of a gas containing a carbon source while flowing through the surface of a catalyst substrate. This process imposes stringent requirements on the choice of catalyst substrate and requires expensive equipment.
The laser evaporation method requires a high-energy-density laser light source and a specific atmosphere in the process of preparing the carbon nanotubes.
In general, these preparation methods require relatively severe reaction conditions. In addition, the preparation of the transition metal modified carbon nanotube is usually realized by adopting a hydrothermal effect between a transition metal precursor and the carbon nanotube, and the reaction requires a long time and subsequent processes such as centrifugation, washing, drying and the like, and needs multiple steps.
[ summary of the invention ]
The invention aims to: aiming at the defects of the prior art, the transition metal modified carbon nanotube material and the preparation method thereof are provided, the method does not need harsh reaction conditions, does not need expensive equipment, directly prepares the transition metal modified carbon nanotube material by a one-step method, and has the advantages of simple and efficient preparation process, easily obtained raw materials and low production cost.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
a preparation method of a transition metal modified carbon nanotube material comprises the following steps:
weighing Fe (NO)3)3·9H2O、Co(NO3)2·6H2O or Ni (NO)3)2·6H2And O, adding cyanamide, performing ultrasonic treatment to obtain a precursor, placing the ark filled with the precursor in a vacuum drying box for drying, finally placing the ark in a tube furnace, calcining under the protection of nitrogen, and naturally cooling to obtain the transition metal modified carbon nanotube.
Further, said Fe (NO)3)3·9H2O、Co(NO3)2·6H2O or Ni (NO)3)2·6H2The dosage ratio of O to cyanamide is 2-4 mmol: 2m L.
Further, the ultrasonic treatment time is 15-60 min.
Further, the drying treatment temperature is 50-70 ℃, and the drying treatment time is 1-2 h.
Further, the calcination treatment is to raise the temperature to 700-1000 ℃ at the rate of 1-2.5 ℃/min and keep the temperature for 0.5-3 h.
The invention also provides the carbon nanotube material prepared by the method.
In summary, due to the adoption of the technical scheme, the invention has the beneficial effects that:
compared with the traditional chemical vapor deposition, the preparation method of the transition metal modified carbon nanotube material does not need harsh reaction conditions and expensive equipment, and can directly prepare the transition metal modified carbon nanotube material by a one-step method, so that the preparation process is simple and efficient, the raw materials are easy to obtain, the production cost is low, and the large-scale production can be realized; the obtained transition metal iron, cobalt and nickel modified carbon nano tube has excellent performance and wide application prospect.
[ description of the drawings ]
FIG. 1 is a scanning electron micrograph (a) and a transmission electron micrograph (b) of Fe/CNT prepared in example 1;
FIG. 2 is a scanning electron micrograph (a) and a transmission electron micrograph (b) of the Co/CNT prepared in example 2;
FIG. 3 shows SEM pictures (a) and TEM pictures (b) of Ni/CNT prepared in example 3.
[ detailed description ] embodiments
Example 1
3mmol of Fe (NO) are weighed3)3·9H2O in the corundum ark, adding 2m L cyanamide, and carrying out ultrasonic treatment for 60min to enable the cyanamide to be adsorbed on Fe (NO)3)3·9H2And (2) surface O, placing the ark filled with the precursor in a vacuum drying oven at 60 ℃ for drying for 1h, finally placing the ark filled with the precursor in a tube furnace, heating to 900 ℃ at the speed of 2 ℃/min under the protection of nitrogen, keeping for 2h, and naturally cooling to obtain the transition metal iron modified carbon nanotube which is marked as Fe/CNT.
The obtained sample is shown in fig. 1, and it can be seen that the interior of the nanotube prepared by ferric nitrate catalysis is of a hollow structure, the tube diameter is about 160nm wide, the inner diameter is about 100nm wide, the tube wall is about 30nm thick, and the tube length is greater than 1 micron. The tube wall is composed of a multi-layer carbon structure.
Example 2
Weighing 4mmol Co (NO)3)2·6H2O in the corundum ark, adding 2m L cyanamide, and carrying out ultrasonic treatment for 15min to enable the cyanamide to be adsorbed on Co (NO)3)2·6H2And (2) surface treatment, placing the ark filled with the precursor in a 50 ℃ vacuum drying oven for drying for 1h, finally placing the ark filled with the precursor in a tube furnace, heating to 700 ℃ at the speed of 2.5 ℃/min under the protection of nitrogen, keeping for 3h, and naturally cooling to obtain the transition metal cobalt modified carbon nanotube which is marked as Co/CNT.
As shown in FIG. 2, it can be seen that the interior of the nanotube prepared by cobalt nitrate catalysis is also hollow, but the diameter of the nanotube is smaller than that of the Fe/CNT tube, the tube diameter is about 100nm wide, the tube wall is thinner, about 3nm thick, and the inner diameter is about 90 nm.
Example 3
Weighing 2mmol of Ni (NO)3)2·6H2Adding 2m L cyanamide into the corundum ark, and performing ultrasonic treatment for 30min to make the cyanamide respectively adsorb on Ni (NO)3)2·6H2And (2) placing the ark filled with the precursor in a vacuum drying oven at 70 ℃ for drying for 2h, finally placing the ark filled with the precursor in a tube furnace, heating to 1000 ℃ at the speed of 1 ℃/min under the protection of nitrogen, keeping the temperature for 0.5h, and naturally cooling to obtain the transition metal nickel modified carbon nanotube which is marked as Ni/CNT.
The obtained sample is shown in FIG. 3, and it can be seen that the interior of the nanotube prepared by nickel nitrate catalysis is also hollow, and is smaller than the tube diameters of the Fe/CNT tube and the Co/CNT tube, the tube diameter is about 50nm wide, the tube wall is about 5nm thick, and the inner diameter is about 40 nm.
The above description is intended to describe in detail the preferred embodiments of the present invention, but the embodiments are not intended to limit the scope of the claims of the present invention, and all equivalent changes and modifications made within the technical spirit of the present invention should fall within the scope of the claims of the present invention.
Claims (6)
1. A preparation method of a transition metal modified carbon nanotube material is characterized by comprising the following steps:
weighing Fe (NO)3)3·9H2O、Co(NO3)2·6H2O or Ni (NO)3)2·6H2And O, adding cyanamide, performing ultrasonic treatment to obtain a precursor, placing the ark filled with the precursor in a vacuum drying box for drying, finally placing the ark in a tube furnace, calcining under the protection of nitrogen, and naturally cooling to obtain the transition metal modified carbon nanotube.
2. The method of making a transition metal modified carbon nanotube material of claim 1, wherein the Fe (NO) is3)3·9H2O、Co(NO3)2·6H2O or Ni (NO)3)2·6H2The dosage ratio of O to cyanamide is 2-4 mmol: 2m L.
3. The method of preparing a transition metal modified carbon nanotube material of claim 1, wherein the sonication time is 15-60 min.
4. The method for preparing a transition metal modified carbon nanotube material of claim 1, wherein the drying treatment temperature is 50-70 ℃ for 1-2 hours.
5. The method as claimed in claim 1, wherein the calcination is carried out at a rate of 1-2.5 ℃/min up to 700-1000 ℃ for 0.5-3 h.
6. Carbon nanotube material produced according to the method of any one of claims 1 to 5.
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| CN112495415A (en) * | 2020-11-20 | 2021-03-16 | 哈尔滨工业大学（深圳） | Nanotube catalytic material and preparation method and application thereof |
| CN113277498A (en) * | 2021-05-19 | 2021-08-20 | 西北工业大学 | Transition metal-based hybrid material nanotube and preparation method and application thereof |
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