CN107673318B - Boron nitride nanotubes and batch preparation method thereof - Google Patents
Boron nitride nanotubes and batch preparation method thereof Download PDFInfo
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- CN107673318B CN107673318B CN201610619062.XA CN201610619062A CN107673318B CN 107673318 B CN107673318 B CN 107673318B CN 201610619062 A CN201610619062 A CN 201610619062A CN 107673318 B CN107673318 B CN 107673318B
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- C01B21/00—Nitrogen; Compounds thereof
- C01B21/06—Binary compounds of nitrogen with metals, with silicon, or with boron, or with carbon, i.e. nitrides; Compounds of nitrogen with more than one metal, silicon or boron
- C01B21/064—Binary compounds of nitrogen with metals, with silicon, or with boron, or with carbon, i.e. nitrides; Compounds of nitrogen with more than one metal, silicon or boron with boron
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- C01P2002/00—Crystal-structural characteristics
- C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
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- C01P2004/03—Particle morphology depicted by an image obtained by SEM
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- C01P2004/60—Particles characterised by their size
- C01P2004/64—Nanometer sized, i.e. from 1-100 nanometer
Abstract
The invention discloses a boron nitride nanotube and a batch preparation method thereof. The preparation method comprises the following steps: using borate as a boron source to support a catalyst to form a precursor, wherein the catalyst comprises a transition metal compound; heating the precursor to 1200-1400 ℃ in a nitrogen-containing atmosphere, carrying out heat preservation reaction in an ammonia atmosphere, and then cooling to room temperature in a protective atmosphere to obtain a crude product; and carrying out post-treatment on the crude product to prepare the boron nitride nanotube. The preparation method of the boron nitride nanotube provided by the invention has the characteristics of low cost, simple process, high yield and the like, is easy to amplify, realizes mass production, simultaneously has the tube diameter of the obtained boron nitride nanotube of 10-150 nm and the tube length of 20-100 microns, and has wide application prospect in the fields of composite materials, heat conduction materials and the like.
Description
Technical Field
The invention particularly relates to a batch preparation method of boron nitride nanotubes, and belongs to the technical field of inorganic nano materials.
Background
Boron Nitride Nanotubes (BNNTs) are a new type of nanomaterial, which not only has a similar crystal structure to Carbon Nanotubes (CNTs), but also has mechanical and thermal conductivity properties comparable to CNTs. In addition, the boron nitride nanotube has excellent oxidation resistance, chemical stability and good insulation. These unique properties make BNNTs have wide applications in the fields of nano-semiconductor devices, hydrogen storage materials, insulating materials, and oxidation-resistant coatings.
The commonly used method for synthesizing the boron nitride nanotube at present comprises an arc discharge method, a laser ablation method, a mechanical ball milling method, a CVD method thermal decomposition method and the like. In recent years, with the intensive research on boron nitride nanotubes, great success and progress have been made in the preparation method. However, the existing preparation processes generally have the defects of high preparation cost or complex equipment and process, certain toxicity of used raw materials, low yield of boron nitride nanotubes and the like.
Disclosure of Invention
The invention mainly aims to provide a boron nitride nanotube and a batch preparation method thereof, so as to overcome the defects in the prior art.
In order to achieve the purpose, the technical scheme adopted by the invention comprises the following steps:
the embodiment of the invention provides a batch preparation method of boron nitride nanotubes, which comprises the following steps:
using borate as a boron source to support a catalyst to form a precursor, wherein the catalyst comprises a transition metal compound;
heating the precursor to 1200-1400 ℃ in a nitrogen-containing atmosphere, carrying out heat preservation reaction in an ammonia atmosphere, then cooling to room temperature in a protective atmosphere to obtain a crude product,
and carrying out post-treatment on the crude product to prepare the boron nitride nanotube.
Furthermore, the diameter of the boron nitride nanotube is 10-150 nm, and the length of the boron nitride nanotube is 20-100 microns.
Compared with the prior art, the preparation method of the boron nitride nanotube provided by the invention has the advantages that cheap and easily-obtained borate is used as a boron source, the boron nitride nanotube is directly obtained on the surface of a precursor (namely the boron source) through the design of a catalyst, other substrates are not needed to be used as a collecting carrier of the boron nitride nanotube, the process is simple, the conditions are easy to control, the cost is low, the batch production can be realized, the yield of the boron nitride nanotube is high, and the obtained boron nitride nanotube has wide application prospects in the fields of composite materials, heat conduction materials and the like.
Drawings
FIGS. 1a-1b are SEM images of boron nitride nanotubes prepared in example 1 of the present invention;
FIG. 2 is a TEM image of boron nitride nanotubes prepared in example 1 of the present invention;
FIG. 3 is a Selected Area Electron Diffraction (SAED) plot of a single boron nitride nanotube of FIG. 2;
FIG. 4 is a Raman spectrum of the boron nitride nanotubes produced in example 1 of the present invention.
Detailed Description
In view of the defects in the prior art, the inventor of the present invention provides a technical scheme of the present invention through long-term research and a great deal of practice, wherein borate is mainly used as a boron source, transition metal salt or oxide or hydroxide thereof and other catalysts are loaded on the surface of the borate through various loading modes, then the borate is placed into chemical vapor deposition equipment, the boron nitride nanotube is obtained through heating and heat preservation reaction in a nitrogen-containing atmosphere and post-treatment. The technical solution, its implementation and principles, etc. will be further explained as follows.
One aspect of an embodiment of the present invention provides a batch preparation method of boron nitride nanotubes, including:
using borate as a boron source to support a catalyst to form a precursor, wherein the catalyst comprises a transition metal compound;
heating the precursor to 1200-1400 ℃ in a nitrogen-containing atmosphere, carrying out heat preservation reaction in an ammonia atmosphere, then cooling to room temperature in a protective atmosphere to obtain a crude product,
and carrying out post-treatment on the crude product to prepare the boron nitride nanotube.
In some embodiments, the method of making comprises: at least one of a ball milling method and an immersion method is selected to make the boron source load the catalyst.
In some preferred embodiments, the preparation method comprises: and mixing the catalyst and a boron source, and carrying out ball milling at the ball milling speed of 200-300 r/min for 100-150 h to obtain the precursor.
Further, borate powder and a transition metal compound can be mixed and placed in a planetary ball mill for ball milling for 100-150 hours at the rotating speed of 200-300 r/min.
In some preferred embodiments, the preparation method comprises: ultrasonically mixing the catalyst and a boron source in a solvent, and then drying to obtain the precursor, wherein the solvent comprises ethanol.
Further, borate powder and ethanol solution of transition metal compound can be ultrasonically mixed for 5-10 hours and then dried.
Further, the borate comprises MgB4O7、Mg2B2O5、Mg3B2O6、CaB4O7And Li2B4O7Any one or a combination of two or more of them, preferably MgB4O7But is not limited thereto.
Further, the transition metal compound includes a transition metal salt or a transition metal oxide.
For example, the transition metal salt includes Fe (NO)3)3、Co(NO3)2And Ni (NO)3)3Any one or a combination of two or more of them. For example, the transition metal oxide includes Fe2O3And CoO, but not limited thereto.
Further, the transition metal compound is preferably Fe (NO)3)3。
Preferably, the molar ratio of the boron element contained in the boron source to the transition metal element contained in the catalyst is 1:0.01 to 0.1.
Further, the nitrogen-containing atmosphere includes an ammonia gas atmosphere or a nitrogen/hydrogen mixed atmosphere.
Further, the protective atmosphere includes hydrogen, nitrogen, or an inert atmosphere (e.g., Ar atmosphere), but may be a mixed atmosphere of two or three of them.
In some preferred embodiments, the preparation method comprises: heating the precursor to 1200-1400 ℃ at a heating rate of 5-15 ℃/min in a nitrogen-containing atmosphere, and then carrying out heat preservation reaction in an ammonia atmosphere.
In some embodiments, the method of making comprises: the post-processing comprises: and sequentially carrying out acid washing and drying treatment on the obtained crude product to obtain the boron nitride nanotube.
In some more specific embodiments, the preparation method comprises: using borate as a boron source to load a metal catalyst or a transition metal compound, then placing the mixture into chemical vapor deposition equipment, heating to 1200-1400 ℃ at a heating rate of 5-15 ℃/min in an ammonia gas or nitrogen and hydrogen mixed atmosphere, then carrying out heat preservation reaction for 0.5-5 h in an ammonia gas atmosphere, cooling to room temperature in a nitrogen or argon atmosphere after heat preservation is finished, obtaining a white crude product, and carrying out acid pickling and drying on the crude product to obtain the boron nitride nanotube.
In a more specific embodiment, the preparation method comprises the following steps:
(1) MgB is added4O7Powder supported catalysts (e.g. Fe (NO)3)3) Then placing the mixture into a high-temperature reaction crucible (such as a high-temperature alumina boat) and then placing the mixture into chemical vapor deposition equipment (such as a tube furnace);
(2) and in the mixed atmosphere of ammonia gas or nitrogen gas and hydrogen gas, raising the temperature to 1100-1400 ℃ by a program, and then preserving the heat for 0.5-5 h to obtain the boron nitride nanotube.
Wherein, MgB4O7And Fe (NO)3)3Is preferably 1: 0.01-1: 0.1.
in another aspect of the embodiment of the invention, the boron nitride nanotube prepared by the method has a tube diameter of 10-150 nm and a tube length of 20-100 microns.
The growth mechanism of the boron nitride nanotube in the invention may be: the boron source is derived from solid magnesium borate. In the ammonia atmosphere, boron is precipitated from the crystal lattice of magnesium borate and dissolved in the catalyst particles attached to the surface, and nitrogen from the decomposition of ammonia is also dissolved in the catalyst particles. When the two elements reach supersaturation, boron and nitrogen are precipitated in a certain proportion to form boron nitride nanotubes, and the boron nitride nanotubes grow on the surfaces of magnesium borate particles by taking a catalyst as a site (see fig. 2).
The preparation method of the boron nitride nanotube provided by the invention has the characteristics of low cost, simple process, high yield, good product crystallinity and the like, is easy to amplify, realizes mass production, and has wide application prospect in the fields of composite materials, heat conduction materials and the like.
The technical scheme of the invention is further explained by combining the attached drawings and a plurality of embodiments.
Example 1: weighing 0.0404gFe (NO)3)3.9H2O and 1.8gMgB4O7Dissolving the powder in 5ml absolute ethyl alcohol, carrying out ultrasonic treatment for 2h, drying at 60 ℃ to obtain faint yellow magnesium borate powder, putting the magnesium borate powder into an alumina boat, putting the alumina boat into a CVD (chemical vapor deposition) furnace, removing air in the furnace chamber by using Ar, and introducing 200sccm NH (ammonium hydroxide)3And (3) programming to 1300 ℃, preserving the temperature for 180min, closing ammonia gas after the reaction is finished, and cooling to room temperature in an argon atmosphere to obtain a white crude product. Please refer to fig. 1a-1b, which are SEM images of boron nitride nanotubes in the prepared crude product, showing that a large amount of boron nitride nanotubes are generated and the boron nitride nanotubes are grown on the surface of magnesium borate. And (3) washing the crude product with hydrochloric acid with the concentration of 1-5 mol/L, performing ultrasonic treatment for 10-12 times, filtering, washing with deionized water for several times, and drying at 60 ℃ for 12 hours to obtain pure boron nitride. Please refer to fig. 2 and fig. 3, which are a TEM image and a Selected Area Electron Diffraction (SAED) image of the prepared boron nitride nanotubes, respectively, showing that the boron nitride nanotubes have good crystallinity.
Example 2: weighing MgB4O7Powder, Fe (NO)3)3Mixing the raw materials according to a molar ratio of 1:0.1, placing the mixture in a planetary ball mill at a set rotating speed of 200-300 r/min, ball-milling the mixture for 150 hours, taking out 1g of the mixture, placing the mixture in an alumina boat in a CVD furnace, removing air in the furnace chamber by using Ar, and introducing 100 standard milliliters per minute (sccm) of N2And H of 100sccm2The temperature was programmed to 1300 ℃. Then N is turned off2And H2Introducing nitrogen of 200sccm, preserving the temperature for 180min, closing ammonia gas after the reaction is finished, and cooling to room temperature in an argon atmosphere. A sample was taken to give a white crude product, which was characterized as boron nitride nanotubes.
Example 3: weighing 0.0404gFe (NO)3)3.9H2O and 1.8gMgB4O7Dissolving the powder in 5ml absolute ethyl alcohol, carrying out ultrasonic treatment for 2h, drying at 60 ℃ to obtain light yellow magnesium borate powder, putting the magnesium borate powder into an alumina boat, placing the alumina boat in a CVD (chemical vapor deposition) furnace, removing air in the furnace chamber by using Ar, and introducing 100 standard milliliters per minute (sccm) of N2And H of 100sccm2Programmed heating to 1300 ℃ and keeping the temperature for 180min, and closing N after the reaction is finished2And H2And cooling to room temperature in argon atmosphere to obtain the white crude product boron nitride nanotube.
Example 4: weighing 0.0404gFe (NO)3)3.9H2O and 1.8gMgB4O7Dissolving the powder in 5ml absolute ethyl alcohol, carrying out ultrasonic treatment for 2h, drying at 60 ℃ to obtain faint yellow magnesium borate powder, putting the magnesium borate powder into an alumina boat, putting the alumina boat into a CVD (chemical vapor deposition) furnace, removing air in the furnace chamber by using Ar, and introducing 200sccm NH (ammonium hydroxide)3And (3) programming to 1200 ℃, preserving the temperature for 180min, closing ammonia gas after the reaction is finished, and cooling to room temperature in an argon atmosphere to obtain a white crude product, namely the boron nitride nanotube.
It should be understood that the above-mentioned embodiments are merely illustrative of the technical concepts and features of the present invention, which are intended to enable those skilled in the art to understand the contents of the present invention and implement the present invention, and therefore, the protection scope of the present invention is not limited thereby. All equivalent changes and modifications made according to the spirit of the present invention should be covered within the protection scope of the present invention.
Claims (9)
1. A batch preparation method of boron nitride nanotubes is characterized by comprising the following steps:
selecting any one of a ball milling method and an immersion method to enable a boron source to load a catalyst to form a precursor, wherein the boron source is borate, and the borate is selected from MgB4O7、Mg2B2O5、Mg3B2O6、CaB4O7And Li2B4O7The catalyst is a transition metal compound, and the molar ratio of boron element contained in the boron source to the transition metal element contained in the catalyst is 1: 0.01-0.1;
heating the precursor to 1200-1400 ℃ at a heating rate of 5-15 ℃/min in a nitrogen-containing atmosphere, carrying out heat preservation reaction in an ammonia atmosphere, and then cooling to room temperature in a protective atmosphere to obtain a crude product;
and carrying out post-treatment on the crude product to prepare the boron nitride nanotube with the tube diameter of 10-150 nm and the tube length of 20-100 microns.
2. The method for mass production of boron nitride nanotubes according to claim 1, comprising: and mixing the catalyst and a boron source, and carrying out ball milling at the ball milling speed of 200-300 r/min for 100-150 h to obtain the precursor.
3. The method for mass production of boron nitride nanotubes according to claim 1, comprising: ultrasonically mixing the catalyst and a boron source in a solvent, and then drying to obtain the precursor, wherein the solvent comprises ethanol.
4. The batch production method of boron nitride nanotubes according to claim 1, characterized in that: the transition metal compound includes a transition metal salt or a transition metal oxide.
5. The batch production method of boron nitride nanotubes according to claim 4, characterized in that: the transition metal salt comprises Fe (NO)3)3、Co(NO3)2And Ni (NO)3)3Any one or a combination of two or more of them.
6. The batch production method of boron nitride nanotubes according to claim 5, characterized in that: the transition metal oxide comprises Fe2O3And CoO, or a combination of both.
7. The batch production method of boron nitride nanotubes according to claim 1, characterized in that: the nitrogen-containing atmosphere includes an ammonia gas atmosphere or a mixed atmosphere of nitrogen and hydrogen.
8. The batch production method of boron nitride nanotubes according to claim 1, characterized in that: the protective atmosphere includes any one of hydrogen and an inert atmosphere.
9. The batch production method of boron nitride nanotubes according to claim 1, wherein the post-treatment comprises: and sequentially carrying out acid washing and drying treatment on the obtained crude product to obtain the boron nitride nanotube.
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| CN111204720A (en) * | 2020-02-10 | 2020-05-29 | 浙江硼矩新材料科技有限公司 | Batch preparation method of boron nitride nanotubes |
| KR102494639B1 (en) * | 2020-08-19 | 2023-02-02 | 내일테크놀로지 주식회사 | Method for preparing nano-materials and apparatus thereof |
| CN113901183A (en) * | 2021-08-20 | 2022-01-07 | 苏州景鹊机器人智能科技有限公司 | Method, device and system for extracting relation words between entities in medical text |
| CN113788464B (en) * | 2021-08-20 | 2022-12-27 | 武汉工程大学 | Method for preparing boron nitride nanotube by using double transition metal oxide as catalyst |
| CN114852976B (en) * | 2022-06-09 | 2023-06-23 | 桂林理工大学 | Hollow boron nitride short rod and preparation method thereof |
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| US9776865B2 (en) * | 2013-11-01 | 2017-10-03 | Bnnt, Llc | Induction-coupled plasma synthesis of boron nitride nanotubes |
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