CN114956088B - Preparation method of boron carbide nanowire - Google Patents
Preparation method of boron carbide nanowire Download PDFInfo
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- 229910052580 B4C Inorganic materials 0.000 title claims abstract description 71
- INAHAJYZKVIDIZ-UHFFFAOYSA-N boron carbide Chemical compound B12B3B4C32B41 INAHAJYZKVIDIZ-UHFFFAOYSA-N 0.000 title claims abstract description 71
- 239000002070 nanowire Substances 0.000 title claims abstract description 62
- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- 238000010438 heat treatment Methods 0.000 claims abstract description 40
- 239000012018 catalyst precursor Substances 0.000 claims abstract description 36
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims abstract description 30
- 238000000034 method Methods 0.000 claims abstract description 28
- 238000003756 stirring Methods 0.000 claims abstract description 22
- 238000006243 chemical reaction Methods 0.000 claims abstract description 18
- 239000012298 atmosphere Substances 0.000 claims abstract description 16
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 14
- 238000005229 chemical vapour deposition Methods 0.000 claims abstract description 12
- 238000001291 vacuum drying Methods 0.000 claims abstract description 12
- 239000012300 argon atmosphere Substances 0.000 claims abstract description 11
- 238000001816 cooling Methods 0.000 claims abstract description 11
- 239000000706 filtrate Substances 0.000 claims abstract description 11
- 238000001914 filtration Methods 0.000 claims abstract description 11
- 239000008367 deionised water Substances 0.000 claims abstract description 10
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 10
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229910002001 transition metal nitrate Inorganic materials 0.000 claims abstract description 9
- 239000002738 chelating agent Substances 0.000 claims abstract description 8
- 239000007789 gas Substances 0.000 claims description 3
- MSMNVXKYCPHLLN-UHFFFAOYSA-N azane;oxalic acid;hydrate Chemical group N.N.O.OC(=O)C(O)=O MSMNVXKYCPHLLN-UHFFFAOYSA-N 0.000 claims description 2
- QGUAJWGNOXCYJF-UHFFFAOYSA-N cobalt dinitrate hexahydrate Chemical compound O.O.O.O.O.O.[Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O QGUAJWGNOXCYJF-UHFFFAOYSA-N 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims description 2
- AOPCKOPZYFFEDA-UHFFFAOYSA-N nickel(2+);dinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O AOPCKOPZYFFEDA-UHFFFAOYSA-N 0.000 claims description 2
- GEVPUGOOGXGPIO-UHFFFAOYSA-N oxalic acid;dihydrate Chemical compound O.O.OC(=O)C(O)=O GEVPUGOOGXGPIO-UHFFFAOYSA-N 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- QZRHHEURPZONJU-UHFFFAOYSA-N iron(2+) dinitrate nonahydrate Chemical compound O.O.O.O.O.O.O.O.O.[Fe+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O QZRHHEURPZONJU-UHFFFAOYSA-N 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 4
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- 239000002086 nanomaterial Substances 0.000 abstract description 3
- 239000000047 product Substances 0.000 description 30
- 230000000052 comparative effect Effects 0.000 description 9
- -1 polytetrafluoroethylene Polymers 0.000 description 8
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 8
- 239000004810 polytetrafluoroethylene Substances 0.000 description 8
- 239000000843 powder Substances 0.000 description 8
- 239000002243 precursor Substances 0.000 description 8
- 229910001220 stainless steel Inorganic materials 0.000 description 8
- 239000010935 stainless steel Substances 0.000 description 8
- 239000013078 crystal Substances 0.000 description 3
- 230000001681 protective effect Effects 0.000 description 3
- 238000001878 scanning electron micrograph Methods 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000011943 nanocatalyst Substances 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 1
- 239000011825 aerospace material Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000005137 deposition process Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- SZQUEWJRBJDHSM-UHFFFAOYSA-N iron(3+);trinitrate;nonahydrate Chemical compound O.O.O.O.O.O.O.O.O.[Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O SZQUEWJRBJDHSM-UHFFFAOYSA-N 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
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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
- C01B32/00—Carbon; Compounds thereof
- C01B32/90—Carbides
- C01B32/914—Carbides of single elements
- C01B32/991—Boron carbide
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- 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
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- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/10—Particle morphology extending in one dimension, e.g. needle-like
- C01P2004/16—Nanowires or nanorods, i.e. solid nanofibres with two nearly equal dimensions between 1-100 nanometer
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- 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
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- 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
- C01P2004/64—Nanometer sized, i.e. from 1-100 nanometer
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- Chemical & Material Sciences (AREA)
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- Nanotechnology (AREA)
- Inorganic Chemistry (AREA)
- Physics & Mathematics (AREA)
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Abstract
The invention discloses a preparation method of boron carbide nanowires, and belongs to the field of inorganic nonmetallic nanomaterials. The method comprises the following steps: sequentially adding boron powder and transition metal nitrate into deionized water, stirring, then adding a chelating agent, continuously stirring, then carrying out hydrothermal reaction, filtering, carrying out vacuum drying and heat treatment under argon atmosphere on the filtrate to obtain a boron-catalyst precursor, placing the obtained boron-catalyst precursor into a chemical vapor deposition furnace, heating to a certain temperature under methane atmosphere to carry out heat treatment reaction, then naturally cooling to room temperature, and carrying out all the reactions to obtain the boron carbide nanowire. The boron carbide nanowire prepared by the method has uniform appearance, large length-diameter ratio and high purity, and the preparation process is simple, high in yield, high in purity and good in repeatability, is easy to realize industrialized mass production, and has wide application prospect in the field of high-performance structural materials.
Description
Technical Field
The invention belongs to the field of inorganic nano materials, and particularly relates to a preparation method of a boron carbide nanowire.
Background
Boron carbide (B) 4 C) The crystal structure is a rhombohedral structure, the lattice of the crystal structure belongs to a D53D-R3m space lattice, and the lattice constant isα=66° 18'. At each of the vertices of the Bravais lattice of rhombohedra, there is a regular icosahedron of 12 atoms, the icosahedrons being covalently bonded to each other and having a crystal orientation [111 ] on the diagonal of the rhombohedra]C-B-C bond in the direction.
The boron carbide is a compound composed of ultra-light elements, the atomic radiuses and the polarizability of B and C elements are close, the covalent bond is strong, the boron carbide nanowire has the characteristics of low density, acid and alkali resistance, excellent mechanical property, high melting point and the like besides the good performance of a typical one-dimensional nanomaterial, and the boron carbide nanowire has very wide application prospect in the field of high-performance structural materials, particularly light high-strength protective materials and aerospace materials.
At present, few reports on boron carbide nanowire synthesis and preparation are provided, and mainly include a carbon nanotube template method/carbothermal reduction method ((1)Renzhi Ma,et al.Chemistry of Materials,2002,14 (10), 4403. (2)Renzhi Ma,et al.Chemical Physics Letters,2002,364 (3-4), 314. (3) Wei Jin. Et al, physical chemistry report, 2004,20 (3), 256. (4)Xinyong Tao,et al.Advanced Materials,22 (18), 2055), a natural plant fiber template method (CN 101850969B), a gas phase reaction method (CN 112794330B) and the like. The method has the defects of low purity, uneven morphology, lower yield, higher production cost, difficult industrial production and the like.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides the preparation method of the boron carbide nanowire with uniform morphology, high purity and large length-diameter ratio, and the preparation method has the advantages of simple preparation process, high yield, good repeatability, easiness in realizing industrial mass production and the like.
In order to achieve the above purpose, the invention adopts the following technical scheme:
the preparation method of the boron carbide nanowire comprises the following specific steps:
(1) Preparing a boron-catalyst precursor: sequentially adding boron powder and transition metal nitrate into deionized water, stirring, continuing to add a chelating agent, uniformly stirring, performing hydrothermal reaction, filtering after the reaction is finished, and performing vacuum drying and heat treatment on the filtrate in an argon atmosphere to obtain a boron-catalyst precursor; the chelating agent is ammonium oxalate monohydrate or oxalic acid dihydrate; the mass ratio of the boron powder to the transition metal nitrate to the chelating agent is 1:0.5 to 2:2 to 5; the heat treatment temperature is 330-410 ℃, and the heat treatment time is 1-2 h;
(2) Preparation of boron carbide nanowires: placing the boron-catalyst precursor obtained in the step (1) in a chemical vapor deposition furnace, heating to a certain temperature in a methane atmosphere for heat treatment reaction, and then naturally cooling to room temperature to obtain boron carbide nanowires; the heat treatment temperature is 1100-1300 ℃, and the heat treatment time is 1-3 h.
In the above scheme, the transition metal nitrate in the step (1) is nickel nitrate hexahydrate, cobalt nitrate hexahydrate or ferric nitrate nonahydrate.
In the scheme, the hydrothermal reaction temperature in the step (1) is 80-120 ℃ and the reaction time is 12-24 h.
In the scheme, the vacuum drying temperature in the step (1) is 80-120 ℃ and the drying time is 12-24 h.
In the scheme, the flow rate of the methane gas in the step (2) is 100-300 ml/min.
In the scheme, in the heat treatment reaction in the step (2), the heating rate is 4-10 ℃/min.
The beneficial effects of the invention are as follows:
1. the invention provides a preparation method of boron carbide nanowires, which comprises the steps of firstly adopting a chelation-hydrothermal reaction combination method to form uniformly dispersed nano catalyst particles on the surface of boron powder; then carrying out low-temperature heat treatment under a protective atmosphere to obtain a boron-catalyst precursor, wherein the heat treatment can effectively remove byproducts generated in the previous reaction and unreacted chelating agent; the protective atmosphere can prevent the nano catalyst from growing up and prevent the boron powder from being oxidized; the formed boron-catalyst precursor is critical to the growth of boron carbide nanowires; and then the boron-catalyst precursor reacts in a chemical vapor deposition system in methane atmosphere, high-temperature methane gas is cracked to provide a carbon source, the boron-catalyst precursor provides a boron source, and under the action of a catalyst, the boron carbide nanowire with uniform appearance, high purity and large length-diameter ratio can be efficiently formed by a dissolution, adsorption, diffusion and deposition process based on a gas-liquid-solid action mechanism.
2. The proper proportion of the transition metal nitrate and the boron powder is favorable for obtaining the boron carbide nanowire, and the boron carbide nanowire cannot be obtained even if the consumption of the transition metal nitrate is too high or too low.
3. The preparation method disclosed by the invention has the advantages of simple process, high yield, high purity and good repeatability, and is easy to realize industrial mass production.
Drawings
Fig. 1 is a high-magnification photograph of a Field Emission Scanning Electron Microscope (FESEM) of the boron carbide nanowire prepared in example 1 of the present invention.
Fig. 2 is a Field Emission Scanning Electron Microscope (FESEM) micrograph of a boron carbide nanowire prepared in example 1 of the present invention.
Fig. 3 is an X-ray diffraction (XRD) pattern of the boron carbide nanowire prepared in example 1 of the present invention.
FIG. 4 is a Scanning Electron Microscope (SEM) photograph of the product obtained in comparative example 1 of the present invention.
FIG. 5 is a Scanning Electron Microscope (SEM) photograph of the product obtained in comparative example 2 of the present invention.
FIG. 6 is a Scanning Electron Microscope (SEM) photograph of the product obtained in comparative example 3 of the present invention.
Detailed Description
For a better understanding of the present invention, the following examples are further illustrated, but are not limited to the following examples.
Example 1
A boron carbide nanowire is prepared by the following method:
(1) Preparing a boron-catalyst precursor: 1.081g B powder, 1.081gNi (NO) were added sequentially to 50ml deionized water 3 ) 2 ·6H 2 O, stirring and then adding 2.162g (NH) 4 ) 2 C 2 O 4 ·H 2 O, after uniformly stirring, placing the solution into a stainless steel reaction kettle with a polytetrafluoroethylene lining for hydrothermal reaction at 80 ℃ for 12 hours, filtering, vacuum drying the filtrate at 80 ℃ for 24 hours, and then carrying out heat treatment at 410 ℃ for 1 hour under an argon atmosphere to obtain a boron-catalyst precursor.
(2) Preparation of boron carbide nanowires: and (3) placing the boron-catalyst precursor obtained in the step (1) in a chemical vapor deposition furnace, heating to 1200 ℃ at a speed of 4 ℃/min in a methane atmosphere with a flow rate of 200ml/min, preserving heat for 3 hours, and then naturally cooling to room temperature, wherein all the precursors react to generate the boron carbide nanowire.
FIGS. 1 and 2 show FESEM high and low power pictures of the boron carbide nanowire product prepared in this example, and FIG. 3 shows XRD patterns of the boron carbide nanowire product prepared in this example, indicating that the product is mainly a well-crystallized boron carbide phase; the boron carbide nanowires have uniform appearance and are all one-dimensional nanowire structures; the length-diameter ratio is large, the diameter is about 65nm, and the length is about 50 mu m.
Comparative example 1
The specific procedure is the same as in example 1, except that the heat treatment atmosphere in step (1) is an air atmosphere. Fig. 4 is an SEM image of the product prepared in comparative example 1, showing that no boron carbide nanowire structure was obtained.
Comparative example 2
The specific procedure is the same as in example 1, except that Ni (NO 3 ) 2 ·6H 2 The amount of O added was 2.5g. Fig. 5 is an SEM image of the product prepared in comparative example 2, showing that no boron carbide nanowire structure was obtained.
Comparative example 3
The specific procedure is the same as in example 1, except that Ni (NO 3 ) 2 ·6H 2 The amount of O added was 0.4g. Fig. 6 is an SEM image of the product prepared in comparative example 3, showing that no boron carbide nanowire structure was obtained.
Example 2
A boron carbide nanowire is prepared by the following method:
(1) Preparing a boron-catalyst precursor: 1.081g g B powder, 0.5405g Co (NO) were added sequentially to 50ml deionized water 3 ) 2 ·6H 2 O, stirring for 30min, then adding 2.162 and 2.162g H 2 C 2 O 4 ·2H 2 O, stirring for 30min, then placing the solution in a stainless steel reaction kettle with a polytetrafluoroethylene lining, performing hydrothermal reaction at 80 ℃ for 24h, filtering, vacuum drying the filtrate at 80 ℃ for 12h, and performing heat treatment at 330 ℃ for 2h in an argon atmosphere to obtain a boron-catalyst precursor.
(2) Preparation of boron carbide nanowires: and (3) placing the boron-catalyst precursor obtained in the step (1) in a chemical vapor deposition furnace, heating to 1300 ℃ at a speed of 10 ℃/min in a methane atmosphere with a flow rate of 300ml/min, preserving heat for 1h, and then naturally cooling to room temperature, wherein all the precursors react to generate the boron carbide nanowire.
The product prepared in this example was characterized by a method similar to that of example 1, and the results show that the product has a structure and morphology similar to those of the product obtained in example 1, and is mainly a well-crystallized boron carbide phase, and the boron carbide nanowires have uniform morphology, large aspect ratio, a diameter of about 72nm and a length of about 60 μm.
Example 3
A boron carbide nanowire is prepared by the following method:
(1) Preparing a boron-catalyst precursor: 1.081g g B powder, 0.5405g Fe (NO) were added sequentially to 50ml deionized water 3 ) 3 ·9H 2 O, stirring for 30min, followed by addition of 5.405g (NH 4 ) 2 C 2 O 4 ·H 2 O, stirring for 30min, then placing the solution in a stainless steel reaction kettle with a polytetrafluoroethylene lining, carrying out hydrothermal reaction at 120 ℃ for 24h, filtering, vacuum drying the filtrate at 120 ℃ for 24h, and then carrying out heat treatment at 410 ℃ for 2h under argon atmosphere to obtain the boron-catalyst precursor.
(2) Preparation of boron carbide nanowires: and (3) placing the boron-catalyst precursor obtained in the step (1) in a chemical vapor deposition furnace, heating to 1100 ℃ at a speed of 4 ℃/min in a methane atmosphere with a flow rate of 100ml/min, preserving heat for 1h, and then naturally cooling to room temperature, wherein all the precursors react to generate the boron carbide nanowire.
The product prepared in this example was characterized by a method similar to that of example 1, and the results show that the product has a structure and morphology similar to those of the product obtained in example 1, and is mainly a well-crystallized boron carbide phase, and the boron carbide nanowires have uniform morphology, large aspect ratio, diameter of about 13nm and length of about 20 μm.
Example 4
A boron carbide nanowire is prepared by the following method:
(1) Preparing a boron-catalyst precursor: 1.081g B powder, 2.162gNi (N) were added sequentially to 50ml deionized waterO 3 ) 2 ·6H 2 O, stirring for 30min, then adding 2.162 and 2.162g H 2 C 2 O 4 ·2H 2 O, stirring for 30min, then placing the solution in a stainless steel reaction kettle with a polytetrafluoroethylene lining, carrying out hydrothermal reaction at 120 ℃ for 12h, filtering, vacuum drying the filtrate at 120 ℃ for 12h, and then carrying out heat treatment at 330 ℃ for 1h under argon atmosphere to obtain the boron-catalyst precursor.
(2) Preparation of boron carbide nanowires: and (3) placing the boron-catalyst precursor obtained in the step (1) in a chemical vapor deposition furnace, heating to 1300 ℃ at a speed of 10 ℃/min in a methane atmosphere with a flow rate of 300ml/min, preserving heat for 3 hours, and then naturally cooling to room temperature, wherein all the precursors react to generate the boron carbide nanowire.
The product prepared in this example was characterized by a method similar to that of example 1, and the results show that the product has a structure and morphology similar to those of the product obtained in example 1, and is mainly a well-crystallized boron carbide phase, and the boron carbide nanowires have uniform morphology, large aspect ratio, diameter of about 88nm and length of about 85 μm.
Example 5
A boron carbide nanowire is prepared by the following method:
(1) Preparing a boron-catalyst precursor: 1.081g g B powder, 2.162g Co (NO) were added sequentially to 50ml deionized water 3 ) 2 ·6H 2 O, stirring for 30min, followed by addition of 5.405g (NH 4 ) 2 C 2 O 4 ·H 2 O, stirring for 30min, then placing the solution in a stainless steel reaction kettle with a polytetrafluoroethylene lining, carrying out hydrothermal reaction at 90 ℃ for 16h, filtering, vacuum drying the filtrate at 110 ℃ for 20h, and then carrying out heat treatment at 350 ℃ for 1h under argon atmosphere to obtain the boron-catalyst precursor.
(2) Preparation of boron carbide nanowires: and (3) placing the boron-catalyst precursor obtained in the step (1) in a chemical vapor deposition furnace, heating to 1100 ℃ at 8 ℃/min in a methane atmosphere with the flow rate of 150ml/min, preserving heat for 3 hours, and then naturally cooling to room temperature, wherein all the precursors react to generate the boron carbide nanowire.
The product prepared in this example was characterized by a method similar to that of example 1, and the results show that the product has a structure and morphology similar to those of the product obtained in example 1, and is mainly a well-crystallized boron carbide phase, and the boron carbide nanowires have uniform morphology, large aspect ratio, diameter of about 32nm and length of about 35 μm.
Example 6
A boron carbide nanowire is prepared by the following method:
(1) Preparing a boron-catalyst precursor: 1.081g g B powder, 1.081g Fe (NO) were added sequentially to 50ml deionized water 3 ) 3 ·9H 2 O, stirring for 30min, then adding 3.243g H 2 C 2 O 4 ·2H 2 O, stirring for 30min, then placing the solution in a stainless steel reaction kettle with a polytetrafluoroethylene lining, performing hydrothermal reaction at 100 ℃ for 18h, filtering, vacuum drying the filtrate at 100 ℃ for 18h, and performing heat treatment at 370 ℃ for 1.5h under argon atmosphere to obtain the boron-catalyst precursor.
(2) Preparation of boron carbide nanowires: and (3) placing the boron-catalyst precursor obtained in the step (1) in a chemical vapor deposition furnace, heating to 1200 ℃ at a speed of 6 ℃/min in a methane atmosphere with a flow rate of 200ml/min, preserving heat for 1h, and then naturally cooling to room temperature, wherein all the precursors react to generate the boron carbide nanowire.
The product prepared in this example was characterized by a method similar to that of example 1, and the results show that the product has a structure and morphology similar to those of the product obtained in example 1, and is mainly a well-crystallized boron carbide phase, and the boron carbide nanowires have uniform morphology, large aspect ratio, diameter of about 44nm and length of about 40 μm.
Example 7
A boron carbide nanowire is prepared by the following method:
(1) Preparing a boron-catalyst precursor: 1.081g B powder, 1.622gNi (NO) were added sequentially to 50ml deionized water 3 ) 2 ·6H 2 O, stirring for 30min, followed by addition of 4.324g (NH 4 ) 2 C 2 O 4 ·H 2 O, stirring for 30min, and placing the solution into a stainless steel reaction kettle with polytetrafluoroethylene liningThe reaction is carried out for 20h by hydrothermal reaction at 110 ℃, the filtration is carried out, the filtrate is dried for 16h in vacuum at 90 ℃, and then the heat treatment is carried out for 2h at 390 ℃ under argon atmosphere, thus obtaining the boron-catalyst precursor.
(2) Preparation of boron carbide nanowires: and (3) placing the boron-catalyst precursor obtained in the step (1) in a chemical vapor deposition furnace, heating to 1100 ℃ at a speed of 4 ℃/min in a methane atmosphere with a flow rate of 250ml/min, preserving heat for 2 hours, and then naturally cooling to room temperature, wherein all the precursors react to generate the boron carbide nanowire.
The product prepared in this example was characterized by a method similar to that of example 1, and the results show that the product has a structure and morphology similar to those of the product obtained in example 1, and is mainly a well-crystallized boron carbide phase, and the boron carbide nanowires have uniform morphology, large aspect ratio, diameter of about 23nm and length of about 30 μm.
Example 8
A boron carbide nanowire is prepared by the following method:
(1) Preparing a boron-catalyst precursor: 1.081g g B powder, 2.162g Fe (NO) were added sequentially to 50ml deionized water 3 ) 3 ·9H 2 O, stirring for 30min, then adding 4.324g H 2 C 2 O 4 ·2H 2 O, stirring for 30min, then placing the solution in a stainless steel reaction kettle with a polytetrafluoroethylene lining, performing hydrothermal reaction at 80 ℃ for 18h, filtering, vacuum drying the filtrate at 120 ℃ for 18h, and performing heat treatment at 410 ℃ for 1.5h under argon atmosphere to obtain the boron-catalyst precursor.
(2) Preparation of boron carbide nanowires: and (3) placing the boron-catalyst precursor obtained in the step (1) in a chemical vapor deposition furnace, heating to 1300 ℃ at a speed of 10 ℃/min in a methane atmosphere with a flow rate of 100ml/min, preserving heat for 2 hours, and then naturally cooling to room temperature, wherein all the precursors react to generate the boron carbide nanowire.
The product prepared in this example was characterized by a method similar to that of example 1, and the results show that the product has a structure and morphology similar to those of the product obtained in example 1, and is mainly a well-crystallized boron carbide phase, and the boron carbide nanowires have uniform morphology, large aspect ratio, diameter of about 78nm and length of about 75 μm.
It is apparent that the above examples are only examples given for clarity of illustration and are not limiting of the embodiments. Other variations or modifications of the above teachings will be apparent to those of ordinary skill in the art. It is not necessary here nor is it exhaustive of all embodiments. And thus obvious variations or modifications to the disclosure are within the scope of the invention.
Claims (6)
1. The preparation method of the boron carbide nanowire is characterized by comprising the following specific steps:
(1) Preparing a boron-catalyst precursor: sequentially adding boron powder and transition metal nitrate into deionized water, stirring, continuing to add a chelating agent, uniformly stirring, performing hydrothermal reaction, filtering after the reaction is finished, and performing vacuum drying and heat treatment on the filtrate in an argon atmosphere to obtain a boron-catalyst precursor; the chelating agent is ammonium oxalate monohydrate or oxalic acid dihydrate; the mass ratio of the boron powder to the transition metal nitrate to the chelating agent is 1:0.5 to 2:2 to 5; the heat treatment temperature is 330-410 ℃, and the heat treatment time is 1-2 h;
(2) Preparation of boron carbide nanowires: placing the boron-catalyst precursor obtained in the step (1) in a chemical vapor deposition furnace, heating to a certain temperature in a methane atmosphere for heat treatment reaction, and then naturally cooling to room temperature to obtain boron carbide nanowires; the heat treatment temperature is 1100-1300 ℃, and the heat treatment time is 1-3 h.
2. The method of claim 1, wherein the transition metal nitrate of step (1) is nickel nitrate hexahydrate, cobalt nitrate hexahydrate or iron nitrate nonahydrate.
3. The preparation method according to claim 1, wherein the hydrothermal reaction temperature in the step (1) is 80-120 ℃ and the reaction time is 12-24 hours.
4. The method according to claim 1, wherein the vacuum drying temperature in step (1) is 80 to 120 ℃ and the drying time is 12 to 24 hours.
5. The method according to claim 1, wherein the flow rate of the methane gas in the step (2) is 100 to 300ml/min.
6. The method according to claim 1, wherein the heating rate in the heat treatment reaction in the step (2) is 4 to 10 ℃/min.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106006644A (en) * | 2016-05-19 | 2016-10-12 | 深圳市鑫成炭素科技有限公司 | Preparation method of nano boron carbide powder |
| CN106882772A (en) * | 2017-04-14 | 2017-06-23 | 武汉理工大学 | A kind of preparation method of the controllable boron nitride nano-tube of caliber |
| CN112794330A (en) * | 2021-01-18 | 2021-05-14 | 黑龙江冠瓷科技有限公司 | Preparation method of boron carbide nanowires |
| CN113788464A (en) * | 2021-08-20 | 2021-12-14 | 武汉工程大学 | Method for preparing boron nitride nanotube by using double transition metal oxide as catalyst |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106006644A (en) * | 2016-05-19 | 2016-10-12 | 深圳市鑫成炭素科技有限公司 | Preparation method of nano boron carbide powder |
| CN106882772A (en) * | 2017-04-14 | 2017-06-23 | 武汉理工大学 | A kind of preparation method of the controllable boron nitride nano-tube of caliber |
| CN112794330A (en) * | 2021-01-18 | 2021-05-14 | 黑龙江冠瓷科技有限公司 | Preparation method of boron carbide nanowires |
| CN113788464A (en) * | 2021-08-20 | 2021-12-14 | 武汉工程大学 | Method for preparing boron nitride nanotube by using double transition metal oxide as catalyst |
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