CN117105185A - Carrier auxiliary preparation method of boron nitride nanotube and boron nitride nanotube - Google Patents
Carrier auxiliary preparation method of boron nitride nanotube and boron nitride nanotube Download PDFInfo
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- CN117105185A CN117105185A CN202311088798.5A CN202311088798A CN117105185A CN 117105185 A CN117105185 A CN 117105185A CN 202311088798 A CN202311088798 A CN 202311088798A CN 117105185 A CN117105185 A CN 117105185A
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- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 title claims abstract description 117
- 229910052582 BN Inorganic materials 0.000 title claims abstract description 75
- 239000002071 nanotube Substances 0.000 title claims abstract description 68
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims abstract description 43
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 36
- 229910052796 boron Inorganic materials 0.000 claims abstract description 31
- 239000003054 catalyst Substances 0.000 claims abstract description 31
- 238000006243 chemical reaction Methods 0.000 claims abstract description 31
- 239000002243 precursor Substances 0.000 claims abstract description 24
- 238000010438 heat treatment Methods 0.000 claims abstract description 23
- 229910052751 metal Inorganic materials 0.000 claims abstract description 22
- 239000002184 metal Substances 0.000 claims abstract description 18
- 239000000203 mixture Substances 0.000 claims abstract description 11
- 238000002156 mixing Methods 0.000 claims abstract description 9
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 56
- 229910052786 argon Inorganic materials 0.000 claims description 28
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims description 14
- 239000008103 glucose Substances 0.000 claims description 14
- 229910052902 vermiculite Inorganic materials 0.000 claims description 13
- 239000010455 vermiculite Substances 0.000 claims description 13
- 235000019354 vermiculite Nutrition 0.000 claims description 13
- GDVKFRBCXAPAQJ-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-]C([O-])=O GDVKFRBCXAPAQJ-UHFFFAOYSA-A 0.000 claims description 12
- 229910001701 hydrotalcite Inorganic materials 0.000 claims description 12
- 229960001545 hydrotalcite Drugs 0.000 claims description 12
- 239000004088 foaming agent Substances 0.000 claims description 11
- 238000004519 manufacturing process Methods 0.000 claims description 11
- 239000002121 nanofiber Substances 0.000 claims description 10
- PZKRHHZKOQZHIO-UHFFFAOYSA-N [B].[B].[Mg] Chemical compound [B].[B].[Mg] PZKRHHZKOQZHIO-UHFFFAOYSA-N 0.000 claims description 5
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 5
- 239000000395 magnesium oxide Substances 0.000 claims description 5
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 5
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims description 5
- 239000007789 gas Substances 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 3
- 238000000034 method Methods 0.000 description 20
- 239000000463 material Substances 0.000 description 13
- 238000005229 chemical vapour deposition Methods 0.000 description 10
- 230000000694 effects Effects 0.000 description 9
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 6
- 239000002041 carbon nanotube Substances 0.000 description 6
- 229910021393 carbon nanotube Inorganic materials 0.000 description 6
- 238000001000 micrograph Methods 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 239000004156 Azodicarbonamide Substances 0.000 description 4
- XOZUGNYVDXMRKW-AATRIKPKSA-N azodicarbonamide Chemical compound NC(=O)\N=N\C(N)=O XOZUGNYVDXMRKW-AATRIKPKSA-N 0.000 description 4
- 235000019399 azodicarbonamide Nutrition 0.000 description 4
- 238000005187 foaming Methods 0.000 description 4
- 239000011148 porous material Substances 0.000 description 4
- 238000001237 Raman spectrum Methods 0.000 description 3
- 229910021529 ammonia Inorganic materials 0.000 description 3
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 description 3
- 229910052810 boron oxide Inorganic materials 0.000 description 3
- JKWMSGQKBLHBQQ-UHFFFAOYSA-N diboron trioxide Chemical compound O=BOB=O JKWMSGQKBLHBQQ-UHFFFAOYSA-N 0.000 description 3
- 239000011777 magnesium Substances 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 238000000137 annealing Methods 0.000 description 2
- 238000000498 ball milling Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000005136 cathodoluminescence Methods 0.000 description 2
- 238000012377 drug delivery Methods 0.000 description 2
- 238000010891 electric arc Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 230000006698 induction Effects 0.000 description 2
- 239000012212 insulator Substances 0.000 description 2
- 238000004093 laser heating Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 125000004433 nitrogen atom Chemical group N* 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 229920006254 polymer film Polymers 0.000 description 2
- 238000004886 process control Methods 0.000 description 2
- 230000000630 rising effect Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000005979 thermal decomposition reaction Methods 0.000 description 2
- MGWGWNFMUOTEHG-UHFFFAOYSA-N 4-(3,5-dimethylphenyl)-1,3-thiazol-2-amine Chemical compound CC1=CC(C)=CC(C=2N=C(N)SC=2)=C1 MGWGWNFMUOTEHG-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 238000001069 Raman spectroscopy Methods 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910021538 borax Inorganic materials 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000002050 diffraction method Methods 0.000 description 1
- UQGFMSUEHSUPRD-UHFFFAOYSA-N disodium;3,7-dioxido-2,4,6,8,9-pentaoxa-1,3,5,7-tetraborabicyclo[3.3.1]nonane Chemical compound [Na+].[Na+].O1B([O-])OB2OB([O-])OB1O2 UQGFMSUEHSUPRD-UHFFFAOYSA-N 0.000 description 1
- 125000002791 glucosyl group Chemical group C1([C@H](O)[C@@H](O)[C@H](O)[C@H](O1)CO)* 0.000 description 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- JCXJVPUVTGWSNB-UHFFFAOYSA-N nitrogen dioxide Inorganic materials O=[N]=O JCXJVPUVTGWSNB-UHFFFAOYSA-N 0.000 description 1
- 235000010339 sodium tetraborate Nutrition 0.000 description 1
- 239000004328 sodium tetraborate Substances 0.000 description 1
- 238000004611 spectroscopical analysis Methods 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
- C01P2002/82—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70 by IR- or Raman-data
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
Abstract
The application discloses a carrier auxiliary preparation method of a boron nitride nanotube and the boron nitride nanotube, wherein the carrier auxiliary preparation method comprises the steps of mixing a boron source and a carrier catalyst component, and putting the mixture into a reactor; heating the interior of the reactor to a reaction temperature under an inert atmosphere to generate a precursor; and placing the inside of the reactor in an ammonia gas atmosphere, maintaining the reaction temperature, and continuously reacting to grow the boron nitride nanotube. The application adopts the carrier to assist in growing the boron nitride nanotube, the carrier can effectively improve the contact area of a boron source and a metal element, improve the generation efficiency of a precursor, correspondingly improve the contact area of the precursor and ammonia gas, obviously improve the growth efficiency of the boron nitride nanotube and realize the purpose of efficiently growing the boron nitride nanotube.
Description
Technical Field
The application belongs to the technical field of nano tube materials, and particularly relates to a carrier auxiliary preparation method of a boron nitride nano tube and the boron nitride nano tube.
Background
Boron nitride nanotubes are hexagonal nanotubes composed of boron and nitrogen atoms, which have a structure similar to carbon nanotubes and have high thermal conductivity and mechanical strength similar to those of carbon nanotubes. Unlike carbon nanotubes, boron nitride nanotubes are insulators, have a band gap of 5.5 to 6.0eV, and have high oxidation resistance in air up to 800 ℃ and an inert atmosphere up to 2800 ℃. Therefore, the boron nitride nanotube has very wide application prospects in the aspects of micro-Electromechanical Systems (MEMs), biomedicine (targeted drug delivery, neutron capture treatment and the like), cathodoluminescence, solid-state neutron detectors and the like. In addition, boron nitride nanotubes can be a very useful nanofiller to improve the thermal conductivity of fibers and polymer films. In addition, boron nitride nanotubes have potential applications in spintronics devices as well as in diverse nano-and microscale electronics.
Currently, methods for synthesizing boron nitride nanotubes mainly include arc discharge, laser heating, induction thermal plasma, chemical Vapor Deposition (CVD). The first three methods all require high temperature and high pressure (5000 ℃/1.4 MPa) growth conditions, which greatly increase production costs and result in boron and nitrogen being combined in an unpredictable manner, resulting in poor product purity. In contrast, CVD processes have good process control, are low cost, and provide high quality boron nitride nanotubes, making them more suitable for industrial fabrication. However, the existing CVD method has lower growth efficiency of the boron nitride nano tube, which has a great relationship with the precursor material and the growth mode. Therefore, how to efficiently prepare the boron nitride nanotubes is the key of the current research.
Disclosure of Invention
The application aims to provide a carrier auxiliary preparation method of a boron nitride nanotube and the boron nitride nanotube, which are used for solving the technical problem of low growth efficiency of the boron nitride nanotube prepared by a CVD method in the prior art.
In order to achieve the above purpose, the application adopts a technical scheme that:
the carrier auxiliary preparation method of the boron nitride nanotube comprises the following steps:
mixing a boron source and a supported catalyst component, and placing the mixture into a reactor;
heating the interior of the reactor to a reaction temperature under an inert atmosphere to generate a precursor;
and placing the inside of the reactor in an ammonia gas atmosphere, maintaining the reaction temperature, and continuously reacting to grow the boron nitride nanotube.
In one or more embodiments, the supported catalyst includes one or a combination of two of vermiculite and hydrotalcite.
In one or more embodiments, the mass ratio of the boron source to the supported catalyst is 1: (1-3).
In one or more embodiments, the supported catalyst includes a support component and a metal catalyst component including one or more combinations of magnesium oxide, iron trichloride, and magnesium boride.
In one or more embodiments, the carrier component includes glucose and a foaming agent.
In one or more embodiments, the mass ratio of the boron source, the glucose, the foaming agent, and the metal catalyst component is 1: (1-5): 0.4: (1-3).
In one or more embodiments, the carrier component includes boron nitride nanofibers.
In one or more embodiments, the mass ratio of the boron source, the boron nitride nanofiber, and the metal catalyst component is 2:1: (0.5-2).
In one or more embodiments, in the step of heating the interior of the reactor to a reaction temperature under an inert atmosphere, the inert atmosphere is specifically argon with a flow of 20-100 standard milliliters per minute, the temperature is specifically increased at a constant speed of 10-30 ℃/min, and the reaction temperature is 1200-1400 ℃;
and in the step of continuously reacting to generate the boron nitride nanotubes by placing the inside of the reactor in an ammonia gas atmosphere, the ammonia gas atmosphere is specifically ammonia gas with the flow of 20-100 standard milliliters per minute, and the reaction time of the continuous reaction is 60-180 minutes.
In order to achieve the above purpose, another technical scheme adopted by the application is as follows:
the boron nitride nanotube prepared by the carrier auxiliary preparation method in any embodiment is provided.
Compared with the prior art, the application has the beneficial effects that:
the application adopts the carrier to assist in growing the boron nitride nanotube, the carrier can effectively improve the contact area of a boron source and a metal element, improve the generation efficiency of a precursor, correspondingly improve the contact area of the precursor and ammonia gas, obviously improve the growth efficiency of the boron nitride nanotube and realize the purpose of efficiently growing the boron nitride nanotube;
the carrier can be prepared from glucose and a foaming agent, wherein the glucose forms a porous structure under the action of the foaming agent when heated to increase the reaction contact area, boron nitride nanofibers can be used to effectively increase the reaction contact area, vermiculite and hydrotalcite rich in metal elements can be used to form a porous structure when heated to increase the reaction contact area, and the rich metal elements can be used as a precursor for a catalyst and a boron source to improve the reaction efficiency.
Drawings
FIG. 1 is a schematic flow chart of an embodiment of a method for preparing boron nitride nanotubes with support assistance according to the present application;
FIG. 2 is an XRD diffraction pattern chart of effect example 1 of the present application;
FIG. 3 is a Raman spectrum of effect example 1 of the present application;
FIG. 4 is a scanning electron microscope image of boron nitride nanotubes prepared in example 1 of the present application;
FIG. 5 is a scanning electron microscope image of boron nitride nanotubes prepared in example 4 of the present application;
FIG. 6 is a scanning electron microscope image of boron nitride nanotubes prepared in example 7 of the present application;
FIG. 7 is a scanning electron microscope image of boron nitride nanotubes prepared in example 8 of the present application;
FIG. 8 is a scanning electron microscope image of boron nitride nanotubes prepared in example 9 of the present application;
FIG. 9 is a scanning electron microscope image of boron nitride nanotubes prepared in example 10 of the present application.
Detailed Description
The present application will be described in detail below with reference to the embodiments shown in the drawings. The embodiments are not intended to limit the application, but structural, methodological, or functional modifications of the application from those skilled in the art are included within the scope of the application.
Boron Nitride Nanotubes (BNNTs) are hexagonal nanotubes composed of boron and nitrogen atoms, which are structurally similar to carbon nanotubes. BNNTs have high thermal conductivity and mechanical strength similar to carbon nanotubes, with young's modulus of-1.2 TPa. Unlike carbon nanotubes, BNNTs are insulators with band gaps of 5.5 to 6.0eV. More importantly, BNNTs have high oxidation resistance in air up to 800 ℃ and in an inert atmosphere up to 2800 ℃.
Therefore, BNTs have very broad application prospects in aspects of micro-Electromechanical Systems (MEMs), biomedicine (targeted drug delivery, neutron capture treatment and the like), cathodoluminescence, solid-state neutron detectors and the like. In addition, BNNTs can also act as a very useful nanofiller that can improve the thermal conductivity of fibers and polymer films. In addition, they have potential applications in spintronics devices as well as in diverse nano-and microscale electronics.
However, the market price of BNNTs is very expensive, which severely hampers their basic research in many fields, mainly due to the low growth efficiency of boron nitride nanotubes and the high manufacturing cost.
The synthesis method of BNTs mainly comprises arc discharge, laser heating, induction thermal plasma, chemical Vapor Deposition (CVD), ball milling and annealing. The growth conditions of the first three methods require high temperatures and pressures (up to 5000 ℃/1.4 MPa), which greatly increases the production costs and results in boron and nitrogen being combined in an unpredictable way, resulting in poor product purity. In contrast, CVD methods have good process control, are low cost, and provide BNNTs of high quality, making them more suitable for industrial manufacturing. In addition, ball milling combined with CVD annealing can improve the growth efficiency of BNNTs. Thus, the CVD method for preparing boron nitride nanotubes is critical for mass production.
However, the existing boron nitride nanotubes have low growth efficiency, which is greatly related to the precursor materials and the growth modes. Therefore, how to efficiently prepare the boron nitride nanotubes is the key of the current research.
In order to improve the synthesis efficiency of the boron nitride nanotubes, the applicant provides a carrier auxiliary preparation method, and the preparation efficiency of the boron nitride nanotubes is improved through the auxiliary effect of the carrier, so that the efficient preparation of the boron nitride nanotubes is realized.
Specifically, referring to fig. 1, fig. 1 is a schematic flow chart of an embodiment of a method for preparing a boron nitride nanotube with support assistance according to the present application.
The auxiliary preparation method of the carrier comprises the following steps:
s100, mixing the boron source and the supported catalyst component, and placing the mixture into a reactor.
And S200, heating the reactor to a reaction temperature in an inert atmosphere to generate a precursor.
S300, placing the reactor in an ammonia gas atmosphere, maintaining the reaction temperature, and continuously reacting to grow the boron nitride nanotube.
In one embodiment, the boron source may be boron powder, and in other embodiments, the boron source may be other boron-containing materials such as boron oxide and sodium tetraborate, or may be a combination of a plurality of boron-containing materials, so that the effects of this embodiment can be achieved.
The carrier catalyst component is used for providing a carrier and a catalyst for reaction, and the catalyst can be uniformly dispersed in the carrier, so that the contact area of the catalyst and a boron source is increased, a precursor is generated efficiently, and meanwhile, the contact area of the precursor and ammonia gas can be increased, the reaction is more thorough and efficient, and the growth efficiency of the boron nitride nanotube is improved.
In one embodiment, the supported catalyst may be a support and catalyst monolith, in particular, the supported catalyst may be vermiculite, hydrotalcite, or a combination of vermiculite and hydrotalcite.
Wherein, the mass ratio of the boron source to the carrier catalyst can be 1: (1-3).
The chemical formula of vermiculite is (Mg,Ca) 0.7 (Mg，Fe，Al) 6.0 (Al，Si) 8.0 (OH 4.8 H 2 o), which is rich in metallic elements; meanwhile, when the vermiculite is roasted at 800-1000 ℃, the volume can be rapidly expanded, the volume can be increased by 6-15 times, the height can be up to 30 times, and rich hole structures can be formed inside the vermiculite.
When the reaction temperature is reached, the boron source can react with the metal element of the vermiculite to generate a precursor in the holes, so that the efficiency of generating the precursor by the reaction of the boron source and the metal element is obviously improved. Correspondingly, the precursor can be fully contacted with ammonia in the hole structure, so that the growth efficiency of the boron nitride nanotube is remarkably improved, and the aim of efficiently growing the boron nitride nanotube is fulfilled.
Hydrotalcite has a chemical formula of [ Mg 6 Al 2 (OH) 16 CO 3 ]·4H 2 O, which is similar to vermiculite, is rich in metallic elements. In addition, hydrotalcite is heated to 450-500 ℃ to generate thermal decomposition, carbonate is completely converted into nitrogen dioxide, and a bimetal composite oxide is generated, meanwhile, in the heating process, the ordered layered structure of hydrotalcite is damaged, the surface area is increased, and the pore volume is increased.
When the reaction temperature is reached, the boron source can react with the metal element in the holes formed by thermal decomposition of hydrotalcite to generate a precursor, so that the efficiency of the reaction of the boron source and the metal element to generate the precursor is obviously improved. Correspondingly, the precursor can be fully contacted with ammonia in the hole structure, so that the growth efficiency of the boron nitride nanotube is remarkably improved, and the aim of efficiently growing the boron nitride nanotube is fulfilled.
In another embodiment, the supported catalyst may also be comprised of separate support components and metal catalyst components, wherein the metal catalyst components may include one or more combinations of magnesium oxide, ferric trichloride, and magnesium boride.
In particular, the carrier component may include glucose and a foaming agent. In the process of heating glucose to a reaction temperature, foaming under the action of a foaming agent to form a porous structure; the boron source can be attached in a pore structure formed by foaming glucose and reacts with the metal element to generate a precursor; correspondingly, the precursor can react with ammonia gas in a pore structure formed by glucose foaming to grow the boron nitride nanotube, so that the precursor generation efficiency and the growth efficiency of the boron nitride nanotube are remarkably improved.
In the above embodiment, azodicarbonamide may be used as the foaming agent, or a type of foaming agent may be used, so that the foaming reaction of glucose during heating may be achieved, and the effect of this embodiment may be achieved.
In the above embodiment, the mass ratio of the boron source, glucose, the foaming agent and the metal catalyst component may be 1: (1-5): 0.4: (1-3).
In another example, the support component may also include boron nitride nanofibers having a rich pore structure and a large specific surface area that facilitate contact of the boron source with the metal catalyst component and contact of the precursor with ammonia gas, significantly improving the precursor generation efficiency and the growth efficiency of the boron nitride nanotubes.
In the above embodiment, the mass ratio of the boron source, the boron nitride nanofiber and the metal catalyst component is 2:1: (0.5-2).
In one embodiment, the inert atmosphere may be argon gas with a flow rate of 20 to 100 standard milliliters per minute; preferably, the inert atmosphere may be embodied as argon gas at a flow rate of 50 standard milliliters per minute.
In one embodiment, the temperature rising process may specifically be a constant temperature rising at a speed of 10 to 30 ℃/min; preferably, the temperature may be raised to the reaction temperature at a constant rate of 20℃per minute.
In one embodiment, the reaction temperature may be specifically 1200 to 1400 ℃; preferably, the reaction temperature may be 1300 ℃.
In one embodiment, the ammonia gas atmosphere may specifically be ammonia gas with a flow rate of 20 to 100 standard milliliters per minute; preferably, the ammonia atmosphere may be embodied as 50 standard milliliters per minute of ammonia gas.
In one embodiment, the reaction time of the continuous reaction may be 60 to 180 minutes; preferably, the duration of the reaction may be 120 minutes.
The beneficial effects of the technical scheme of the present application are explained in further detail below in conjunction with specific embodiments.
Example 1:
a boron nitride nanotube is prepared by the following method:
boron powder and vermiculite are mixed according to the following proportion of 1:1, putting the mixture into a tube furnace, introducing 50sccm argon, and heating to 1300 ℃;
and then closing argon, introducing 50sccm ammonia gas, preserving heat for 120min, and growing to obtain the boron nitride nanotube.
Example 2:
a boron nitride nanotube is prepared by the following method:
boron powder and vermiculite are mixed according to the following proportion of 1:1, putting the mixture into a tube furnace, introducing 100sccm argon, and heating to 1200 ℃;
and then closing argon, introducing 100sccm ammonia gas, preserving heat for 60min, and growing to obtain the boron nitride nanotube.
Example 3:
a boron nitride nanotube is prepared by the following method:
boron powder and vermiculite are mixed according to the following proportion of 1:3, mixing the materials according to the mass ratio, putting the materials into a tube furnace, introducing 20sccm argon, and heating to 1400 ℃;
and then closing argon, introducing 20sccm ammonia gas, preserving heat for 180min, and growing to obtain the boron nitride nanotube.
Example 4:
a boron nitride nanotube is prepared by the following method:
boron powder and hydrotalcite are mixed according to the following proportion of 1:1, putting the mixture into a tube furnace, introducing 50sccm argon, and heating to 1300 ℃;
and then closing argon, introducing 50sccm ammonia gas, preserving heat for 120min, and growing to obtain the boron nitride nanotube.
Example 5:
a boron nitride nanotube is prepared by the following method:
boron powder and hydrotalcite are mixed according to the following proportion of 1:1, putting the mixture into a tube furnace, introducing 100sccm argon, and heating to 1200 ℃;
and then closing argon, introducing 100sccm ammonia gas, preserving heat for 60min, and growing to obtain the boron nitride nanotube.
Example 6:
a boron nitride nanotube is prepared by the following method:
boron powder and hydrotalcite are mixed according to the following proportion of 1:3, mixing the materials according to the mass ratio, putting the materials into a tube furnace, introducing 20sccm argon, and heating to 1400 ℃;
and then closing argon, introducing 20sccm ammonia gas, preserving heat for 180min, and growing to obtain the boron nitride nanotube.
Example 7:
a boron nitride nanotube is prepared by the following method:
boron powder, glucose, azodicarbonamide and magnesium oxide are mixed according to the following ratio of 1:3:0.4:2, mixing the materials according to the mass ratio, putting the materials into a tube furnace, introducing 50sccm argon, and heating to 1300 ℃;
and then closing argon, introducing 50sccm ammonia gas, preserving heat for 120min, and growing to obtain the boron nitride nanotube.
Example 8:
a boron nitride nanotube is prepared by the following method:
boron powder, glucose, azodicarbonamide and ferric trichloride are mixed according to the following ratio of 1:5:0.4:3, mixing the materials according to the mass ratio, putting the materials into a tube furnace, introducing 100sccm argon, and heating to 1200 ℃;
and then closing argon, introducing 100sccm ammonia gas, preserving heat for 60min, and growing to obtain the boron nitride nanotube.
Example 9:
a boron nitride nanotube is prepared by the following method:
boron oxide, glucose, azodicarbonamide and magnesium boride are mixed according to a ratio of 1:1:0.4:1, putting the mixture into a tube furnace, introducing 20sccm argon, and heating to 1400 ℃;
and then closing argon, introducing 20sccm ammonia gas, preserving heat for 180min, and growing to obtain the boron nitride nanotube.
Example 10:
a boron nitride nanotube is prepared by the following method:
boron powder, boron oxide, boron nitride nanofiber and ferric trichloride are mixed according to the following ratio of 1:1:1:1, putting the mixture into a tube furnace, introducing 50sccm argon, and heating to 1300 ℃;
and then closing argon, introducing 50sccm ammonia gas, preserving heat for 120min, and growing to obtain the boron nitride nanotube.
Example 11:
a boron nitride nanotube is prepared by the following method:
boron powder, boron nitride nanofiber and magnesium oxide are mixed according to the following ratio of 2:1: mixing at a mass ratio of 0.5, placing into a tube furnace, introducing 100sccm argon, and heating to 1200 ℃;
and then closing argon, introducing 100sccm ammonia gas, preserving heat for 60min, and growing to obtain the boron nitride nanotube.
Example 12:
a boron nitride nanotube is prepared by the following method:
boron powder, boron nitride nanofiber and magnesium boride are mixed according to the following ratio of 2:1:2, putting the mixture into a tube furnace, introducing 20sccm argon, and heating to 1400 ℃;
and then closing argon, introducing 20sccm ammonia gas, preserving heat for 180min, and growing to obtain the boron nitride nanotube.
Effect example 1:
XRD diffractometry was performed on the boron nitride nanotubes prepared in examples 1, 4, 7, and 10, resulting in fig. 2.
Referring to fig. 2, fig. 2 is an XRD diffractogram of effect example 1 of the present application. As shown in the figure, XRD diffraction patterns of the boron nitride nanotubes prepared in examples 1, 4, 7 and 10 all show characteristic signals of h-BN as 5 peaks of (002), (100), (101), (102) and (110) planes, and the characteristic signals correspond to the characteristic signals of h-BN in JCPDS card (No. 73-2095), so that the grown sample is proved to be a pure h-BN structure.
Raman spectroscopic analysis was performed on the boron nitride nanotubes prepared in examples 1, 4 and 7, to obtain fig. 3.
Referring to fig. 3, fig. 3 is a raman spectrum of effect example 1 of the present application. As shown in the drawings, embodiments1. The Raman spectra of the boron nitride nanotubes prepared by 4 and 7 are all shown at 1368cm -1 There is a strong absorption band, which is related to the E2g in-plane vibration mode of h-BN.
From the above experiments, it was found that the high purity boron nitride nanotubes were grown in examples 1, 4, 7 and 10.
Effect example 2:
characterization analysis was performed on the boron nitride nanotubes prepared in examples 1, 4, 7, 8, 9, 10, resulting in fig. 4, 5, 6, 7, 8, 9.
Referring to fig. 4 to 9, fig. 4 is a scanning electron microscope of the boron nitride nanotube prepared in example 1 of the present application, fig. 5 is a scanning electron microscope of the boron nitride nanotube prepared in example 4 of the present application, fig. 6 is a scanning electron microscope of the boron nitride nanotube prepared in example 7 of the present application, fig. 7 is a scanning electron microscope of the boron nitride nanotube prepared in example 8 of the present application, fig. 8 is a scanning electron microscope of the boron nitride nanotube prepared in example 9 of the present application, and fig. 9 is a scanning electron microscope of the boron nitride nanotube prepared in example 10 of the present application.
As shown in the figure, a large number of high quality boron nitride nanotubes were grown in the porous structure prepared in example 7; examples 1, 4, 8, 9, 10 all produced a large number of high quality boron nitride nanotubes.
From the above experiments, it was found that the high quality boron nitride nanotubes were grown in examples 1, 4, 7, 8, 9, and 10.
The previous description of the disclosure is provided to enable any person skilled in the art to make or use the disclosure. Various modifications to the disclosure will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other variations without departing from the scope of the disclosure. Thus, the disclosure is not limited to the examples and designs described herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
Claims (10)
1. The carrier-assisted preparation method of the boron nitride nanotube is characterized by comprising the following steps of:
mixing a boron source and a supported catalyst component, and placing the mixture into a reactor;
heating the interior of the reactor to a reaction temperature under an inert atmosphere to generate a precursor;
and placing the inside of the reactor in an ammonia gas atmosphere, maintaining the reaction temperature, and continuously reacting to grow the boron nitride nanotube.
2. The support-assisted preparation method according to claim 1, wherein the supported catalyst comprises one or a combination of two of vermiculite and hydrotalcite.
3. The carrier-assisted preparation method according to claim 2, wherein the mass ratio of the boron source to the carrier catalyst is 1: (1-3).
4. The carrier-assisted manufacturing method of claim 1, wherein the carrier catalyst comprises a carrier component and a metal catalyst component comprising one or more combinations of magnesium oxide, iron trichloride, and magnesium boride.
5. The carrier-assisted manufacturing method of claim 4, wherein the carrier component includes glucose and a foaming agent.
6. The carrier-assisted manufacturing method according to claim 5, wherein the mass ratio of the boron source, the glucose, the foaming agent and the metal catalyst component is 1: (1-5): 0.4: (1-3).
7. The carrier-assisted manufacturing method of claim 4, wherein the carrier component includes boron nitride nanofibers.
8. The carrier-assisted manufacturing method of claim 7, wherein the mass ratio of the boron source, the boron nitride nanofiber and the metal catalyst component is 2:1: (0.5-2).
9. The carrier-assisted preparation method according to claim 1, wherein in the step of heating the inside of the reactor to a reaction temperature under an inert atmosphere, the inert atmosphere is specifically argon gas with a flow rate of 20-100 standard milliliters per minute, the heating is specifically uniform heating at a speed of 10-30 ℃/min, and the reaction temperature is 1200-1400 ℃;
and in the step of continuously reacting to generate the boron nitride nanotubes by placing the inside of the reactor in an ammonia gas atmosphere, the ammonia gas atmosphere is specifically ammonia gas with the flow of 20-100 standard milliliters per minute, and the reaction time of the continuous reaction is 60-180 minutes.
10. A boron nitride nanotube prepared by the carrier-assisted preparation method of any one of claims 1 to 9.
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