CN113788464A - Method for preparing boron nitride nanotube by using double transition metal oxide as catalyst - Google Patents
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Abstract
The invention discloses a method for preparing a boron nitride nanotube by catalyzing a double-transition metal oxide, belonging to the field of inorganic nano materials. The method comprises the following steps: 1) sequentially adding boron powder, two transition metal nitrates and a precipitator into deionized water, uniformly stirring, carrying out hydrothermal reaction, filtering, vacuum drying, and then carrying out heat treatment for 1-3 h at the temperature of 280-300 ℃ in an air atmosphere to obtain a double transition metal oxide-boron precursor; 2) and placing the obtained double-transition metal oxide-boron precursor in a chemical vapor deposition system, heating to a certain temperature in an ammonia atmosphere for heat treatment reaction, and then naturally cooling to room temperature to obtain the high-quality boron nitride nanotube. According to the method, the double transition metal oxide is used as a catalyst, the obtained boron nitride nanotube has high purity, does not contain impurities such as boron nitride particles and the like, and has high yield; the preparation method is simple, has good repeatability, and can realize batch and stable preparation of the boron nitride nanotube.
Description
Technical Field
The invention belongs to the field of inorganic nano materials, and particularly relates to a method for preparing a boron nitride nanotube by catalyzing a double-transition metal oxide.
Background
Boron nitride nanotubes have received a great deal of attention from scientists in the fields of materials, physics, chemistry and interdiscipline due to their excellent mechanical, thermal and electrical properties (Pakdel a, et al. Such as: the strength and Young's modulus of the boron nitride nanotubes are both significantly higher than those of engineering ceramics and glass, and even comparable to diamond (Falin A, et al. nat Commun.,2017,8,15815.Wei X L, et al. adv Mater.,2010,22, 4895); it also has unique elasto-plastic deformation capability-boron nitride nanotubes can recover their original form after several bends without significant defects (Golberg D, et al. Well-crystallized, less-defective boron nitride nanotubes can exist stably in an air atmosphere at 900 ℃ (Golberg D, et al. script mater, 2001,44,1561.Zhi C Y, et al. mat Sci Eng r.,2010,70, 92).
The excellent properties of the boron nitride nanotube make the boron nitride nanotube become a very promising inorganic nano additive in the field of high-performance composite materials (such as ceramic matrix composite materials, metal matrix composite materials and polymer matrix composite materials). Such as: boron nitride nanotubes are added to advanced structural ceramic materials such as silicon nitride (Li T F, et al, ceramic. int.,2018,44,6456), silicon carbide (Zhu G X, et al, J Eur cer soc.,2018,38,4614), zirconia (Tatarko P, et al, J Eur cer soc.,2014,34,1829), alumina (Wang W L, et al, J Am cer soc.,2011,94, 3636J Eur cer soc.,2011,31,2277), and the like, and the bending strength and fracture toughness of the ceramic materials are both significantly improved. For metal matrix composite materials, after boron nitride nanotubes are added into aluminum matrix composite materials, the bending strength, hardness and elastic modulus of the materials can be obviously improved (Nautiyal P, et al. adv Eng mater, 2016,18,1747.Antillon M, et al. adv Eng mater, 2018,20,1800122), and the aluminum matrix composite materials containing the boron nitride nanotubes have wide application prospects in the aspects of light and super-strong structural materials for aerospace (Yamaguchi M, et al. acta mater, 2012,60,6213.BishT A, et al. Mat Sci Eng A.,2018,710,366). After adding boron nitride nanotubes to the polymer material, the tensile strength, elastic modulus and thermal conductivity of the composite material (such as boron nitride nanotube-polystyrene (Zhi C Y, et al.j Mater res.,2006,21,2794), boron nitride nanotube-polyvinyl alcohol (Zhou S J, et al.nanotechnology,2012,23,055708), boron nitride nanotube-polycarbonate (Lin S Q, et al.new J chem.,2017,41,7571)) are all greatly improved.
The boron nitride nanotube has already made a certain research progress in the aspect of improving the performance of the composite material, but the preparation of the boron nitride nanotube with high quality, high purity and high yield is still one of the main problems limiting the large-scale application of the boron nitride nanotube. The thermal catalytic chemical vapor deposition method is the most common method for preparing the boron nitride nanotube, and the main principle is as follows: under the action of transition metal (iron, cobalt or nickel) oxide catalyst, boron and nitrogen atoms form boron nitride nanotube through "nucleation-growth" step based on "gas-liquid-solid" mechanism. However, when a single transition metal is used for preparing the boron nitride nanotube, the problems of low catalytic efficiency, low purity of the obtained boron nitride nanotube, easy generation of granular boron nitride and the like exist generally.
Disclosure of Invention
The invention aims to provide a method for preparing a boron nitride nanotube by using a double-transition metal oxide catalyst, wherein the method takes a nano-scale double-transition metal oxide as a catalyst, and the obtained boron nitride nanotube has high purity, does not contain impurities such as boron nitride particles and the like, and has high yield; the preparation method is simple, has good repeatability, and can realize batch and stable preparation of the boron nitride nanotube.
In order to solve the technical problems, the technical scheme adopted by the invention is as follows:
the method for preparing the boron nitride nanotube by using the double transition metal oxide as a catalyst comprises the following specific steps:
(1) preparation of a double transition metal oxide-boron precursor: sequentially adding boron powder, two transition metal nitrates and a precipitator into deionized water, uniformly stirring, carrying out hydrothermal reaction, filtering and vacuum drying after the reaction is finished, and then carrying out heat treatment on the dried powder in an air atmosphere to obtain a double transition metal oxide-boron precursor, wherein the heat treatment temperature is 280-300 ℃ and the time is 1-3 hours;
(2) preparing the boron nitride nanotube: and (2) placing the double-transition metal oxide-boron precursor obtained in the step (1) in a chemical vapor deposition system, heating to a certain temperature in an ammonia atmosphere for heat treatment reaction, and then naturally cooling to room temperature to obtain the high-quality boron nitride nanotube.
In the above scheme, in the step (1), the transition metal nitrate is ferric nitrate nonahydrate, cobalt nitrate hexahydrate or nickel nitrate hexahydrate.
In the above scheme, in the step (1), the precipitant is urea or ammonium carbonate.
In the above scheme, in the step (1), the molar ratio of the two transition metal nitrates is 1: 2,
in the above scheme, in the step (1), the molar ratio of the obtained double transition metal oxide, boron powder and precipitant is: 1: (50-100): (5-10), wherein the obtained double transition metal oxide is obtained by theoretical conversion of two transition metal nitrates.
In the scheme, in the step (1), the hydrothermal reaction temperature is 110-130 ℃ and the time is 12-24 hours.
In the scheme, in the step (1), the temperature of vacuum drying is 80-120 ℃, and the time is 12-24 hours.
In the scheme, in the step (2), the flow rate of the ammonia gas is 100-200 ml/min.
In the scheme, in the step (2), the heat treatment reaction temperature is 1200-1400 ℃, and the reaction time is 1-3 h.
The invention has the beneficial effects that:
1. firstly, carrying out hydrothermal reaction and low-temperature heat treatment on boron powder, two transition metal nitrates and a precipitator to obtain a nanoscale double-transition metal oxide uniformly distributed on the surface of the boron powder, and then carrying out high-temperature catalytic reaction in an ammonia atmosphere by taking the nanoscale double-transition metal oxide as a catalyst to obtain a high-quality boron nitride nanotube; the obtained product is a pure white boron nitride nanotube, has high purity, does not contain impurities such as boron nitride particles and the like, has high yield and large length-diameter ratio, is simple in preparation method, and can realize batch and stable preparation of the boron nitride nanotube.
2. The nanometer-scale double-transition metal oxide is prepared through hydrothermal reaction and low-temperature heat treatment, the reaction condition is mild, the preparation method is simple, and the obtained nanometer-scale double-transition metal oxide is uniformly distributed on the surface of boron powder; the nanometer double transition metal oxide is used as a catalyst, the catalytic effect is remarkable, on one hand, the nanometer size can better adsorb boron atoms and nitrogen atoms and provide more boron nitride nucleation sites, and on the other hand, the two transition metals are mutually promoted, so that the catalytic performance of the nanometer double transition metal oxide is favorably improved, and the growth of a boron nitride nanotube is promoted; the obtained boron nitride nanotube has high purity and high yield.
Drawings
Fig. 1 is a Scanning Electron Microscope (SEM) picture of boron nitride nanotubes prepared in example 1 of the present invention.
Fig. 2 is an X-ray diffraction (XRD) pattern of the double transition metal oxide-boron precursor prepared in example 1 of the present invention.
Fig. 3 is an SEM picture of a double transition metal oxide-boron precursor prepared in example 1 of the present invention.
FIG. 4 is an SEM picture of boron nitride nanotubes prepared in example 2 of the present invention.
FIG. 5 is an SEM picture of boron nitride nanotubes prepared in example 3 of the present invention.
Detailed Description
In order to better understand the present invention, the following examples are further provided to illustrate the present invention, but the present invention is not limited to the following examples.
Example 1
A method for preparing a boron nitride nanotube by using a double transition metal oxide catalyst comprises the following specific steps:
(1) preparation of a double transition metal oxide-boron precursor: sequentially adding 50ml of deionized water, 0.25mol of boron powder, 0.0025mol of nickel nitrate hexahydrate, 0.005mol of ferric nitrate nonahydrate and 0.025mol of urea into a hydrothermal reaction kettle, magnetically stirring, carrying out hydrothermal reaction at 110 ℃ for 24 hours, filtering, carrying out vacuum drying at 80 ℃ for 24 hours, and carrying out heat treatment on the dried powder at 300 ℃ in an air atmosphere for 3 hours to obtain the double-transition metal oxide-boron (NiFe)2O4-B) a precursor.
(2) Preparing the boron nitride nanotube: and (2) paving the double transition metal oxide-boron precursor obtained in the step (1) in a high-purity corundum crucible, placing the corundum crucible in a chemical vapor deposition system, carrying out heat treatment at 1400 ℃ for 1h under ammonia gas flow with the flow rate of 100ml/min, and then naturally cooling to room temperature, wherein the precursor is completely converted into a pure white boron nitride nanotube, and the purity and the yield are high.
FIG. 1 is an SEM image of the boron nitride nanotubes prepared in this example, which shows that the products are high purity and free of particulate impurities, and are boron nitride nanotubes with one-dimensional nanostructures, and the nanotubes have uniform tube diameter, large length-diameter ratio, diameter of about 50nm, and length of over 10 μm. FIGS. 2 and 3 are an XRD pattern and an SEM image of the Bitransition metal oxide-boron precursor prepared in this example, respectively, showing that the synthesized catalyst is a nano-sized Bitransition metal oxide (NiFe)2O4)。
Example 2
A method for preparing a boron nitride nanotube by using a double transition metal oxide catalyst comprises the following specific steps:
(1) preparation of a double transition metal oxide-boron precursor: sequentially adding 50ml of deionized water, 0.25mol of boron powder, 0.0025mol of cobalt nitrate hexahydrate, 0.005mol of ferric nitrate nonahydrate and 0.025mol of ammonium carbonate into a hydrothermal reaction kettle, magnetically stirring, carrying out hydrothermal reaction at 130 ℃ for 12 hours, filtering, carrying out vacuum drying at 110 ℃ for 12 hours, and carrying out heat treatment on the dried powder at 280 ℃ for 3 hours in an air atmosphere to obtain the double transition metal oxide-boron (CoFe)2O4-B) precursors。
(2) Preparing the boron nitride nanotube: and (2) placing the double transition metal oxide-boron precursor obtained in the step (1) in a chemical vapor deposition system, carrying out heat treatment at 1200 ℃ for 3h under the ammonia gas flow with the flow rate of 200ml/min, and then naturally cooling to room temperature to obtain the high-quality pure white boron nitride nanotube.
Fig. 4 is an SEM picture of the boron nitride nanotubes prepared in this example, which shows that the product purity is high, no particulate impurities exist, the boron nitride nanotubes are all one-dimensional structures, the tube diameters of the nanotubes are uniform, the diameters are about 65nm, and the lengths exceed 10 μm. XRD characterization of the double transition metal oxide-boron precursor prepared in this example using a method similar to that of example 1 revealed that the synthesized catalyst was a nano-sized double transition metal oxide (CoFe)2O4)。
Example 3
A method for preparing a boron nitride nanotube by using a double transition metal oxide catalyst comprises the following specific steps:
(1) preparation of a double transition metal oxide-boron precursor: sequentially adding 50ml of deionized water, 0.25mol of boron powder, 0.0025mol of ferric nitrate nonahydrate, 0.005mol of cobalt nitrate hexahydrate and 0.0125mol of urea into a hydrothermal reaction kettle, magnetically stirring, carrying out hydrothermal reaction at 130 ℃ for 24 hours, filtering, carrying out vacuum drying at 110 ℃ for 24 hours, and carrying out heat treatment on the dried powder at 300 ℃ in an air atmosphere for 3 hours to obtain the double transition metal oxide-boron (FeCo)2O4-B) a precursor.
(2) Preparing the boron nitride nanotube: and (2) placing the double transition metal oxide-boron precursor obtained in the step (1) in a chemical vapor deposition system, carrying out heat treatment at 1400 ℃ for 3h under the ammonia gas flow with the flow rate of 100ml/min, and then naturally cooling to room temperature to obtain the high-quality pure white boron nitride nanotube.
Fig. 5 is an SEM picture of the boron nitride nanotubes prepared in this example, which shows that the product purity is high, no particulate impurities exist, the boron nitride nanotubes are all one-dimensional structures, the tube diameters of the nanotubes are uniform, the diameters are about 90nm, and the lengths exceed 10 μm. The Bitransition metal oxide-boron precursor prepared in this example was treated in a similar manner to that of example 1XRD characterization of the precursor shows that the synthesized catalyst is nanometer level double transition metal oxide (FeCo)2O4)。
Example 4
A method for preparing a boron nitride nanotube by using a double transition metal oxide catalyst comprises the following specific steps:
(1) preparation of a double transition metal oxide-boron precursor: sequentially adding 50ml of deionized water, 0.25mol of boron powder, 0.0025mol of cobalt nitrate hexahydrate, 0.005mol of nickel nitrate hexahydrate and 0.0125mol of ammonium carbonate into a hydrothermal reaction kettle, magnetically stirring, then carrying out hydrothermal reaction at 110 ℃ for 12 hours, filtering, vacuum drying at 80 ℃ for 12 hours, and carrying out heat treatment on the dried powder for 1 hour at 280 ℃ in an air atmosphere to obtain the double transition metal oxide-boron (NiCo)2O4-B) a precursor.
(2) Preparing the boron nitride nanotube: and (2) placing the double transition metal oxide-boron precursor obtained in the step (1) in a chemical vapor deposition system, carrying out heat treatment for 1h at 1400 ℃ under the ammonia gas flow with the flow rate of 100ml/min, and then naturally cooling to room temperature to obtain the high-quality pure white boron nitride nanotube.
The product prepared in the embodiment is characterized by adopting a method similar to that of the embodiment 1, and the result shows that the product has high purity and no granular impurities, and is a boron nitride nanotube with a one-dimensional structure, the diameter of the nanotube is uniform, the diameter is about 10nm, and the length is more than 20 μm. XRD characterization of the Bitransition metal oxide-boron precursor prepared in this example using a method similar to that of example 1 indicated that the synthesized catalyst was a nano-sized Bitransition metal oxide (NiCo)2O4)。
Example 5
A method for preparing a boron nitride nanotube by using a double transition metal oxide catalyst comprises the following specific steps:
(1) preparation of a double transition metal oxide-boron precursor: adding 50ml of deionized water, 0.125mol of boron powder, 0.0025mol of nickel nitrate hexahydrate, 0.005mol of ferric nitrate nonahydrate and 0.025mol of ammonium carbonate into a hydrothermal reaction kettle in sequence, magnetically stirring, carrying out hydrothermal reaction at 115 ℃ for 18h, filtering, and vacuum drying at 100 ℃ for 18h, wherein the dried powder is air gas at 285 ℃Heat treating for 2.5h under atmosphere to obtain double transition metal oxide-boron (NiFe)2O4-B) a precursor.
(2) Preparing the boron nitride nanotube: and (2) placing the double transition metal oxide-boron precursor obtained in the step (1) in a chemical vapor deposition system, performing heat treatment at 1250 ℃ for 1.5h under the flow of ammonia gas with the flow rate of 130ml/min, and then naturally cooling to room temperature to obtain the high-quality boron nitride nanotube.
The product prepared in the embodiment is characterized by adopting a method similar to that of the embodiment 1, and the result shows that the product has high purity and no granular impurities, and is a boron nitride nanotube with a one-dimensional structure, the diameter of the nanotube is uniform, the diameter is about 30nm, and the length is more than 15 μm. XRD characterization of the Bitransition metal oxide-boron precursor prepared in this example using a method similar to that of example 1 indicated that the synthesized catalyst was a nano-sized Bitransition metal oxide (NiFe)2O4)。
Example 6
A method for preparing a boron nitride nanotube by using a double transition metal oxide catalyst comprises the following specific steps:
(1) preparation of a double transition metal oxide-boron precursor: sequentially adding 50ml of deionized water, 0.125mol of boron powder, 0.0025mol of cobalt nitrate hexahydrate, 0.005mol of ferric nitrate nonahydrate and 0.025mol of urea into a hydrothermal reaction kettle, magnetically stirring, carrying out hydrothermal reaction at 120 ℃ for 18 hours, filtering, carrying out vacuum drying at 100 ℃ for 24 hours, and carrying out heat treatment on the dried powder at 290 ℃ for 2 hours to obtain the double transition metal oxide-boron (CoFe)2O4-B) a precursor.
(2) Preparing the boron nitride nanotube: and (2) placing the double transition metal oxide-boron precursor obtained in the step (1) in a chemical vapor deposition system, carrying out heat treatment at 1300 ℃ for 2h under the flow of ammonia gas with the flow rate of 150ml/min, and then naturally cooling to room temperature to obtain the high-quality boron nitride nanotube.
The product prepared in the example is characterized by adopting a method similar to that of example 1, and the result shows that the product has high purity and no granular impurities, and is a boron nitride nanotube with a one-dimensional structure, the diameter of the nanotube is uniform, and the diameter of the nanotube is about 35nmAnd a length exceeding 20 μm. XRD characterization of the double transition metal oxide-boron precursor prepared in this example using a method similar to that of example 1 revealed that the synthesized catalyst was a nano-sized double transition metal oxide (CoFe)2O4)。
Example 7
A method for preparing a boron nitride nanotube by using a double transition metal oxide catalyst comprises the following specific steps:
(1) preparation of a double transition metal oxide-boron precursor: sequentially adding 50ml of deionized water, 0.125mol of boron powder, 0.0025mol of ferric nitrate nonahydrate, 0.005mol of cobalt nitrate hexahydrate and 0.0125mol of ammonium carbonate into a hydrothermal reaction kettle, magnetically stirring, carrying out hydrothermal reaction at 125 ℃ for 18h, filtering, vacuum drying at 90 ℃ for 18h, and carrying out heat treatment on the dried powder for 1.5h at 295 ℃ in air atmosphere to obtain the double-transition metal oxide-boron (FeCo)2O4-B) a precursor.
(2) Preparing the boron nitride nanotube: and (2) placing the double transition metal oxide-boron precursor obtained in the step (1) in a chemical vapor deposition system, carrying out heat treatment at 1350 ℃ for 2.5h under the flow of ammonia gas with the flow rate of 180ml/min, and then naturally cooling to room temperature to obtain the high-quality pure white boron nitride nanotube.
The product prepared in the embodiment is characterized by adopting a method similar to that of the embodiment 1, and the result shows that the product has high purity and no granular impurities, and is a boron nitride nanotube with a one-dimensional structure, the diameter of the nanotube is uniform, the diameter is about 70nm, and the length is more than 5 μm. XRD characterization of the double transition metal oxide-boron precursor prepared in this example using a method similar to that of example 1 revealed that the synthesized catalyst was a nano-sized double transition metal oxide (FeCo)2O4)。
Example 8
A method for preparing a boron nitride nanotube by using a double transition metal oxide catalyst comprises the following specific steps:
(1) preparation of a double transition metal oxide-boron precursor: adding 50ml of deionized water, 0.125mol of boron powder, 0.0025mol of cobalt nitrate hexahydrate, 0.005mol of nickel nitrate hexahydrate and 0.0125mol of urea into a hydrothermal reaction kettle in sequence,magnetically stirring, performing hydrothermal reaction at 120 deg.C for 24 hr, filtering, vacuum drying at 90 deg.C for 12 hr, and heat treating the dried powder at 280 deg.C in air atmosphere for 2 hr to obtain double transition metal oxide-boron (NiCo)2O4-B) a precursor.
(2) Preparing the boron nitride nanotube: and (2) placing the double transition metal oxide-boron precursor obtained in the step (1) in a chemical vapor deposition system, carrying out heat treatment at 1400 ℃ for 3h under the ammonia gas flow with the flow rate of 200ml/min, and then naturally cooling to room temperature to obtain the high-quality pure white boron nitride nanotube.
The product prepared in the embodiment is characterized by adopting a method similar to that of the embodiment 1, and the result shows that the product has high purity and no granular impurities, and is a boron nitride nanotube with a one-dimensional structure, the diameter of the nanotube is uniform, the diameter is about 60nm, and the length is more than 30 μm. XRD characterization of the Bitransition metal oxide-boron precursor prepared in this example using a method similar to that of example 1 indicated that the synthesized catalyst was a nano-sized Bitransition metal oxide (NiCo)2O4)。
It is apparent that the above embodiments are only examples for clearly illustrating and do not limit the embodiments. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. And are neither required nor exhaustive of all embodiments. And obvious variations or modifications are therefore intended to be included within the scope of the invention as claimed.
Claims (9)
1. A method for preparing a boron nitride nanotube by using a double transition metal oxide catalyst is characterized by comprising the following specific steps:
(1) preparation of a double transition metal oxide-boron precursor: sequentially adding boron powder, two transition metal nitrates and a precipitator into deionized water, uniformly stirring, carrying out hydrothermal reaction, filtering and vacuum drying after the reaction is finished, and then carrying out heat treatment on the dried powder in an air atmosphere to obtain a double transition metal oxide-boron precursor, wherein the heat treatment temperature is 280-300 ℃ and the time is 1-3 hours;
(2) preparing the boron nitride nanotube: and (2) placing the double-transition metal oxide-boron precursor obtained in the step (1) in a chemical vapor deposition system, heating to a certain temperature in an ammonia atmosphere for heat treatment reaction, and then naturally cooling to room temperature to obtain the high-quality boron nitride nanotube.
2. The method according to claim 1, wherein in the step (1), the transition metal nitrate is iron nitrate nonahydrate, cobalt nitrate hexahydrate or nickel nitrate hexahydrate.
3. The method according to claim 1, wherein in the step (1), the precipitant is urea or ammonium carbonate.
4. The method according to claim 1, wherein in the step (1), the molar ratio of the two transition metal nitrates is 1: 2.
5. the method according to claim 1, wherein in the step (1), the molar ratio of the double transition metal oxide, the boron powder and the precipitating agent is: 1: (50-100): (5-10), wherein the obtained double transition metal oxide is obtained by theoretical conversion of two transition metal nitrates.
6. The method according to claim 1, wherein in the step (1), the hydrothermal reaction temperature is 110-130 ℃ and the hydrothermal reaction time is 12-24 h.
7. The method according to claim 1, wherein in the step (1), the temperature of the vacuum drying is 80-120 ℃ and the time is 12-24 h.
8. The method according to claim 1, wherein the flow rate of the ammonia gas in the step (2) is 100 to 200 ml/min.
9. The method according to claim 1, wherein in the step (2), the heat treatment reaction temperature is 1200-1400 ℃ and the reaction time is 1-3 h.
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| CN111747386A (en) * | 2020-06-28 | 2020-10-09 | 武汉工程大学 | Morphology-controllable boron nitride nanostructure-graphene composite material and preparation method thereof |
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| US20130029131A1 (en) * | 2009-09-21 | 2013-01-31 | Deakin University | Method of manufacture |
| US20150329360A1 (en) * | 2014-05-14 | 2015-11-19 | University Of Dayton | Growth of silicon and boron nitride nanomaterials on carbon fibers by chemical vapor deposition |
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| CN111747385A (en) * | 2020-06-28 | 2020-10-09 | 武汉工程大学 | In-situ synthesis boron nitride nanosheet-nanotube composite material and preparation method thereof |
| CN111747386A (en) * | 2020-06-28 | 2020-10-09 | 武汉工程大学 | Morphology-controllable boron nitride nanostructure-graphene composite material and preparation method thereof |
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| CN114956088A (en) * | 2022-05-05 | 2022-08-30 | 武汉工程大学 | Preparation method of boron carbide nanowires |
| CN114956088B (en) * | 2022-05-05 | 2023-11-14 | 武汉工程大学 | Preparation method of boron carbide nanowire |
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