CN108483413B - Preparation method of bamboo-shaped boron nitride nanotube hierarchical structure with ultrathin boron nitride nanosheets loaded on surface - Google Patents
Preparation method of bamboo-shaped boron nitride nanotube hierarchical structure with ultrathin boron nitride nanosheets loaded on surface Download PDFInfo
- Publication number
- CN108483413B CN108483413B CN201810216476.7A CN201810216476A CN108483413B CN 108483413 B CN108483413 B CN 108483413B CN 201810216476 A CN201810216476 A CN 201810216476A CN 108483413 B CN108483413 B CN 108483413B
- Authority
- CN
- China
- Prior art keywords
- boron nitride
- bamboo
- hierarchical structure
- loaded
- ultrathin
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Images
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
- C01B21/0646—Preparation by pyrolysis of boron and nitrogen containing compounds
-
- 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
- C01P2002/01—Crystal-structural characteristics depicted by a TEM-image
-
- 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
- C01P2002/85—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70 by XPS, EDX or EDAX 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
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/04—Particle morphology depicted by an image obtained by TEM, STEM, STM or AFM
-
- C—CHEMISTRY; METALLURGY
- 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
- C01P2004/13—Nanotubes
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/20—Particle morphology extending in two dimensions, e.g. plate-like
- C01P2004/24—Nanoplates, i.e. plate-like particles with a thickness from 1-100 nanometer
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/50—Agglomerated particles
-
- 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
-
- 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
- C01P2004/62—Submicrometer sized, i.e. from 0.1-1 micrometer
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Nanotechnology (AREA)
- Inorganic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Manufacturing & Machinery (AREA)
- Crystallography & Structural Chemistry (AREA)
- Catalysts (AREA)
- Crystals, And After-Treatments Of Crystals (AREA)
Abstract
The invention relates to a preparation method of a bamboo-shaped boron nitride nanotube hierarchical structure with ultrathin boron nitride nanosheets loaded on the surface. Firstly, the raw materials are uniformly mixed according to the molar ratio and then poured into a stainless steel ball milling tank. And flatly paving the ball-milled product at the bottom of the alumina ceramic boat, and then placing the substrate at the upper end of the ceramic boat into a tube furnace. Adjusting the heating rate, temperature, atmosphere and heat preservation time of the tube furnace, taking out the substrate after the reaction to obtain a crude product, and purifying to obtain the bamboo-shaped boron nitride nanotube hierarchical structure powder with the ultrathin nanosheets loaded on the surface. The method has the advantages of simple process, low price of raw materials, good crystallinity, high purity, high yield of the prepared product, good photoluminescence performance and good adsorption performance on methylene blue, and the hierarchical structure of the bamboo-shaped boron nitride nanotube with the surface loaded with the ultrathin nanosheets has important application prospects in the fields of photocatalysis and hydrogen storage.
Description
Technical Field
The invention belongs to the technical field of new materials, and relates to a preparation method of a bamboo-shaped boron nitride nanotube hierarchical structure with ultrathin boron nitride nanosheets loaded on the surface, which is mainly applied to the technical fields of photoluminescent materials, photocatalytic materials, hydrogen storage materials and preparation methods thereof.
Technical Field
Boron Nitride (BN) is similar in structure to graphite, but also has many excellent physicochemical properties compared to graphite, such as: high heat resistance, high thermal conductivity, excellent dielectric properties (good high-temperature insulation), good high-temperature stability, low thermal expansion coefficient, good lubricity, chemical stability (excellent corrosion resistance), and the like. Since Chotra et al synthesized boron nitride nanotubes by plasma arc discharge, their unique electrical properties and promising applications in nanotechnology have attracted the interest of more and more researchers. Boron Nitride Nanotubes (BNNTs) have excellent mechanical properties, the elastic modulus of about 1TPa, excellent high-temperature oxidation resistance, strong ferromagnetism, excellent blue-violet light emitting performance and excellent hydrogen storage performance, thereby having great application value in the aspects of electronics, high-temperature lubrication, novel composite materials and the like.
At present, BNNTs with different morphologies have been prepared by different methods. As for the preparation method of BNNTs, arc discharge method, ball-milling annealing method, template method, Chemical Vapor Deposition (CVD), self-propagating (SHS) assisted annealing method, high-pressure benzene thermal method, coprecipitation-annealing method, oxide assisted method, etc. have been reported. ZHONG et al prepared two crystal forms of bamboo-shaped BNNTs with high yield by Chemical Vapor Deposition (CVD), the band gap width of which is not affected by the crystal forms, and the ultraviolet visible light and cathode luminescence spectrum results of the sample show that the sample has two absorption peaks 266.4nm (4.65eV) and 214.3nm (5.79eV) in the ultraviolet region. The WangJilin and the like prepare BNNTs with different structures such as corrugated type, hollow type, horn type, bamboo joint type and the like by a high-temperature self-propagating auxiliary annealing method, and the method has great potential in the aspect of preparing BN nanotubes with different structures in a large amount and in a controllable manner at low cost. Zhang et al successfully synthesize a one-dimensional boron nitride nanorod with a BN nanosheet-containing surface by using a high-pressure benzene thermal method, and researches find that the hierarchical structure shows excellent hydrogen storage performance, so that the method provides a new idea for the BN hierarchical structure. And (3) mixing the Xiaofan and the like with a B/N precursor uniformly by using a coprecipitation method catalyst, and then further annealing to obtain the one-dimensional BN nanotube. The Li Juan and the like collect high-purity BNNTs with good crystallization on a stainless steel substrate through an oxygen-assisted high-temperature annealing method, and the BN nano tube has good photoluminescence performance and potential application prospect in the field of long-wavelength luminescence. Tatarko et al toughens zirconia ceramics with BNNTs by a discharge plasma sintering method, the fracture toughness of the zirconia-BNNTs ceramics is gradually improved with the increase of the addition amount of BNNTs, and when the addition amount of BNNTs is 2.5%, the fracture toughness of the composite ceramics is almost doubled.
Although the report can successfully synthesize BNNTs, the problems of high cost, high energy consumption, low yield and the like exist, and the obtained material is mostly a one-dimensional material, so that the structural form, the crystal form and the application aspect of the boron nitride nanotube are paid more attention. The BN material with a hierarchical structure has wide application prospect in the aspects of adsorption, catalyst carrier, hydrogen storage, ultraviolet luminescence and the like due to large specific surface area, and can also be used for strengthening and toughening high polymers, inorganic materials, metal materials and the like. However, few reports have been made to date on methods for preparing hierarchical boron nitride nanotube materials with high specific surface areas, such as ultrathin nanosheets supported by boron nitride nanotubes.
Disclosure of Invention
The invention aims to provide a preparation method of a bamboo-shaped boron nitride nanotube hierarchical structure with ultrathin boron nitride nanosheets loaded on the surface.
The main ideas of the invention are as follows: ammonium pentaborate, ammonia borane complex and magnesium oxide are used as raw materials. Firstly, the raw materials are uniformly mixed according to the molar ratio, and the mixture is poured into a stainless steel ball milling tank and vacuumized. And cooling after ball milling for a period of time, and taking out the coarse ground product. Uniformly spreading the ball-milled product on the bottom of an alumina ceramic boat, and covering an alumina substrate on the upper end of the ceramic boat. Then the ceramic boat is put into a tube furnace, the temperature rise rate of the tube furnace is adjusted to 10 ℃/min, the temperature rises to 1000-1250 ℃ in the flowing ammonia atmosphere, and the temperature is automatically reduced after being preserved for a period of time. And taking out the white flocculent product loaded on the alumina substrate, and purifying to obtain the bamboo-shaped boron nitride nanotube hierarchical structure powder loaded with the ultrathin nanosheets on the surface.
According to the scheme, the molar ratio NH of the ammonium borate to the ammonia borane complex to the magnesium oxide4B5O8：NH3BH3: MgO is 1: (6-10): (1-4).
According to the scheme, the ball milling process is carried out by revolving at 50-100 rpm, and the ratio of revolution to rotation is 1: 2, the ball milling pot and the ball milling material are ZrO2The ball milling time is 3-6 h.
According to the scheme, the substrate for collecting the crude product is a high-purity alumina substrate.
According to the scheme, the temperature rise rate of the tubular furnace in the annealing process is 10 ℃/min, the annealing temperature is 1000-1250 ℃, the heat preservation time is 3-10h, and the ammonia flow rate is 0.3-1L/min.
According to the scheme, the process for collecting the crude product comprises the step of placing the alumina substrate loaded with the crude product in absolute ethyl alcohol for ultrasonic treatment for 30-60min to obtain the boron nitride suspension.
According to the scheme, the purification process of the crude product comprises the steps of adding 5mol/L hydrochloric acid into the suspension, then carrying out hot stirring at 80 ℃ for 6-24h, filtering, washing with absolute ethyl alcohol, and finally drying at 80 ℃ for 10-24h under a vacuum condition to obtain the bamboo-shaped boron nitride nanotube hierarchical structure powder with the ultrathin nanosheets loaded on the surface.
According to the scheme, the tube diameter range of the bamboo-shaped boron nitride nanotube hierarchical structure sample with the surface loaded with the ultrathin nanosheets is 0.2-1 mu m, and the length of the sample is more than 5 mu m. The interior of the nanotube is in a periodic bamboo joint structure, the inner diameter range is 40-300nm, and a large number of ultrathin hBN nano sheets are loaded on the exterior. The average thickness of the nano-sheet is about 13nm, and the thickness of the whole boron nitride nano-sheet is 50-200 nm.
The preparation method disclosed by the invention is simple and reliable in preparation process, green and environment-friendly, the used raw materials are low in price, the prepared product is good in crystallinity, high in purity and yield, good in photoluminescence performance and good in methylene blue adsorption performance, and the prepared hierarchical structure of the bamboo-joint boron nitride nanotube has an important application prospect in the fields of photocatalysis and hydrogen storage.
The invention takes ammonium pentaborate and ammonia borane complex as boron source, and the chemical reaction proposed to occur in the synthesis process of the hierarchical structure of the bamboo-shaped boron nitride nanotube with the surface loaded with the ultrathin nanosheets is as follows:
NH4B5O8(s)→B2O3(l)+NH3(g)+H2O(g) (1)
[NH3·BH3]n(s)→NH3(g)+B*(g)+H2(g) (2)
NH3(g)→N*(g)+H2(g) (3)
B2O3(l)+B*(g)→B2O2(g) (4)
MgO(s)+B*(g)→Mg(g)+B2O2(g) (5)
B*(g)+N*(g)+Mg(g)+B2O2(g)→[B-N-Mg-O] (6)
[B-N-Mg-O]+Al2O3substrat→BN nanotubes(BNNTs)+Mg/MgO (7)
BNNTs+B2O2(g)+B*(g)+N*(g)+H2(g)→BNNTs-BN nanoplates(BNNT-BNNPs)(s)+H2O(g)+H2(g) (8)
in the invention, the possible reaction mechanism for preparing the hierarchical structure of the bamboo-joint boron nitride nanotube with the surface loaded with the ultrathin nanosheets is as follows: with the gradual rise of the temperature, the solid ammonium pentaborate is decomposed at high temperature to generate liquid B2O3And NH3Gas (formula 1), ammonia borane complex generates active B, N and H at high temperature2(formula 2 and formula 3), activity B and formed B2O3The liquid surface reacts to generate gaseous intermediate B2O2(as in formula 4). As the temperature increases, the catalyst MgO is reduced to Mg vapor (formula 5). Gas phases B, N, B2O2With Mg vapor rising into contact with Al2O3Final formation of substrate [ B-N-Mg-O ]]Solid solutions (formula 6). The metal solid solution continuously absorbs B, N atoms, and after the concentration reaches saturation, solid-phase crystals start to gradually form BN crystal nuclei on the surfaces of the liquid drops. According to the VLS growth mechanism, bamboo-like BNNTs begin to form (formula 7) under the action of surface stress. With further extension of the annealing time, the catalyst loses activity and BNNTs growth stops. At the same time, gaseous substances such as active Nx, B, H around BNNTs2And the surface layer of the nanotubes is further eroded to form defects. These defects can act as active growth sites, and N and B that have not reacted to completion can also further deposit BN lamellae on these active sites according to the VS growth mechanism. This periodic process does not stop until the external B or N source is consumed. Finally, with BN nano-meterThe tube wall of the tube is eroded to different degrees, and the thickness of the formed BN nano-flake is different (formula 7).
Drawings
FIG. 1 is an X-ray diffraction (XRD) spectrum of a hierarchical structure of a bamboo-shaped boron nitride nanotube with ultrathin nanosheets loaded on the surface.
FIG. 2 is a scanning electron microscope (FE-SEM) photograph of a hierarchical structure of a bamboo-like boron nitride nanotube with ultrathin nanosheets loaded on the surface.
FIG. 3 is an X-ray energy spectrum (EDS) diagram of a hierarchical structure of a bamboo-shaped boron nitride nanotube with ultrathin nanosheets loaded on the surface.
Fig. 4 is a Transmission Electron Microscope (TEM) photograph and a High Resolution Transmission Electron Microscope (HRTEM) photograph of a hierarchical structure of the bamboo-shaped boron nitride nanotube with the ultrathin nanosheets loaded on the surface.
Detailed Description
For better understanding of the present invention, the contents of the present invention will be further illustrated with reference to examples, but the contents of the present invention are not limited to only the following examples:
x-ray diffraction analysis (XRD) of the product obtained in the following example Using an X-ray powder diffractometer type Rigaku D/MAX-LLIA
2 theta is 10-90 degrees; observing the morphology with a scanning electron microscope (FSEM) model S-4800; the microstructure inside the sample was studied with a JEM2100-F Transmission Electron Microscope (TEM), and the product was ultrasonically dispersed in absolute ethanol and dropped onto a copper mesh. X-ray energy spectrometers use S-4800 scanning electron microscopy (FSEM) with its own EDS.
Example 1
2.00g of ammonium pentaborate, 1.85g of ammonia borane complex and 0.40g of magnesium oxide were weighed out (molar ratio 1:6: 1). Firstly, uniformly mixing raw materials, pouring the mixture into a stainless steel ball milling tank and vacuumizing; cooling after ball milling for 6h, and taking out a coarse grinding product; uniformly spreading the ball-milled product on the bottom of an alumina ceramic boat, and covering an alumina substrate on the upper end of the ceramic boat; then putting the ceramic boat into a tube furnace, adjusting the temperature rise rate of the tube furnace to 10 ℃/min, raising the temperature to 1200 ℃ in a flowing ammonia atmosphere, and automatically reducing the temperature after heat preservation for 6 h; taking out the alumina substrate loaded with the white flocculent product, and placing the alumina substrate in absolute ethyl alcohol for 30min by ultrasonic treatment to obtain a boron nitride suspension; and adding 20ml of 5mol/L hydrochloric acid into the suspension, then carrying out hot stirring at 80 ℃ for 12h, filtering, washing with absolute ethyl alcohol, and finally drying under the vacuum condition of 80 ℃ for 24h to obtain the hierarchical structure powder of the bamboo-shaped boron nitride nanotube with the surface loaded with the ultrathin nanosheets.
The XRD spectrum of the prepared boron nitride sample is shown in the attached figure 1. As can be seen from fig. 1, the XRD spectrum has six distinct main peaks, and the diffraction peaks at 2 θ ═ 26.6 °, 42.5 °, 43.8 °, 50.0 °, 54.9 ° and 75.9 ° coincide with those of hexagonal boron nitride, indicating that the product is a well-crystallized h-BN crystal.
The sample is in a one-dimensional linear hierarchical structure, the length is more than 5 mu m, the diameter range is 200-800nm, and the content is more than 96%. The surface was loaded with a large number of nanoplatelets, with a single platelet thickness of about 13nm (fig. 2 c). The sheets were bent and folded, and the thickness of the entire boron nitride sheet, which was formed by interweaving the sheets, was about 50-200nm (FIGS. 2a and 2 d). Secondly, it is noted that the one-dimensional linear hierarchical structure is essentially hollow in the middle, with internal tube diameters varying from 40 to 300nm (indicated by white arrows in fig. 2a and 2 d). The unique three-dimensional hierarchical hollow structure has relatively high specific surface area and has potential application prospect in the fields of adsorption, surface modification and functionalization, hydrogen storage and material toughening.
FIG. 3 shows that the sample contains B, N, O elements and the O element may be caused by the sample being oxidized or adsorbing water in the air, as a result of the surface scanning analysis of the single boron nitride nanotube hierarchical structure.
FIG. 4 TEM and HRTEM pictures of hierarchical structures of boron nitride nanotubes. As can be seen from fig. 4(a), the macroscopic diameter of the hierarchical structure was about 1mm, the BN nanosheets were supported by one layer thick on the surface, and the intermediate nanotube structure was almost not clearly seen. FIG. 4(b) shows the hierarchical structure of the bamboo-type boron nitride nanotube with a small number of nano-flakes loaded on the surface of the whole nanotube with the diameter of about 200 nm. With reference to fig. 4(c), it can be clearly observed that the product is a one-dimensional hollow bamboo-like structure, the single hollow tube cavities are connected with each other and are not communicated with each other, and the diameter of the cavity is about 50 nm. The surface of the nanotube is loaded with flake BN, and the length of each flake ranges from 50nm to 80nm (shown by a white frame). Fig. 4(d) is an HRTEM photograph of a hierarchically structured surface flake from which clear lattice fringes can be observed with a lattice spacing of about 0.34nm, which is consistent with the lattice constant of the hexagonal boron nitride (002) crystal plane, indicating that the flake has better crystallinity.
Example 2
A preparation method of a bamboo-shaped boron nitride nanotube hierarchical structure with ultrathin boron nitride nanosheets loaded on the surface comprises the following steps:
2.00g of ammonium pentaborate, 2.47g of ammonia borane complex and 0.40g of magnesium oxide were weighed out (molar ratio 1:8: 1). Firstly, uniformly mixing raw materials, pouring the mixture into a stainless steel ball milling tank and vacuumizing; cooling after ball milling for 3h, and taking out a coarse grinding product; uniformly spreading the ball-milled product on the bottom of an alumina ceramic boat, and covering an alumina substrate on the upper end of the ceramic boat; then putting the ceramic boat into a tube furnace, adjusting the temperature rise rate of the tube furnace to 10 ℃/min, raising the temperature to 1000 ℃ in a flowing ammonia atmosphere, preserving the temperature for 10h, and then automatically cooling; taking out the alumina substrate loaded with the white flocculent product, and placing the alumina substrate in absolute ethyl alcohol for ultrasonic treatment for 60min to obtain a boron nitride suspension; and adding 20ml of 5mol/L hydrochloric acid into the suspension, then carrying out hot stirring at 80 ℃ for 24h, filtering, washing with absolute ethyl alcohol, and finally drying under the vacuum condition of 80 ℃ for 24h to obtain the hierarchical structure powder of the bamboo-shaped boron nitride nanotube with the surface loaded with the ultrathin nanosheets.
The product is analyzed by XRD, FSEM and TEM/HRTEM, and the yield of the bamboo-shaped boron nitride nanotube hierarchical structure sample with the ultrathin nanosheets loaded on the surface is more than 85%, the diameter range is 0.1-1.2 mu m, and the length is more than 3 mu m. The interior of the nanotube is of a periodic bamboo-shaped structure, the inner diameter range is 50-300nm, and the average inner diameter is 80 nm; a large number of ultrathin hBN nano sheets are loaded outside, the average thickness of the nano sheets is about 10nm, the thickness range of the whole boron nitride nano sheet layer is 30-250nm, and the average thickness is about 100 nm.
Example 3
A preparation method of a bamboo-shaped boron nitride nanotube hierarchical structure with ultrathin boron nitride nanosheets loaded on the surface comprises the following steps:
2.00g of ammonium pentaborate, 2.47g of ammonia borane complex and 1.60g of magnesium oxide were weighed out (molar ratio 1:8: 4). Firstly, uniformly mixing raw materials, pouring the mixture into a stainless steel ball milling tank and vacuumizing; cooling after ball milling for 5h, and taking out a coarse grinding product; uniformly spreading the ball-milled product on the bottom of an alumina ceramic boat, and covering an alumina substrate on the upper end of the ceramic boat; then putting the ceramic boat into a tube furnace, adjusting the heating rate of the tube furnace to 10 ℃/min, heating to 1100 ℃ in a flowing ammonia atmosphere, and automatically cooling after heat preservation for 8 h; taking out the alumina substrate loaded with the white flocculent product, and placing the alumina substrate in absolute ethyl alcohol for ultrasonic treatment for 60min to obtain a boron nitride suspension; and adding 80ml of 5mol/L hydrochloric acid into the suspension, then carrying out hot stirring at 80 ℃ for 12h, filtering, washing with absolute ethyl alcohol, and finally drying under the vacuum condition of 80 ℃ for 24h to obtain the hierarchical structure powder of the bamboo-shaped boron nitride nanotube with the surface loaded with the ultrathin nanosheets.
The product is analyzed by XRD, FSEM and TEM/HRTEM, and the yield of the bamboo-shaped boron nitride nanotube hierarchical structure sample with the ultrathin nanosheets loaded on the surface is more than 90%, the diameter range of the sample is 0.1-1.0 μm, and the length of the sample is more than 3 μm. The interior of the nanotube is of a periodic bamboo-shaped structure, the inner diameter range is 50-300nm, and the average inner diameter is 80 nm; a large number of ultrathin hBN nano sheets are loaded outside, the average thickness of the nano sheets is about 15nm, the thickness range of the whole boron nitride nano sheet layer is 50-250nm, and the average thickness is about 100 nm.
Example 4
A preparation method of a bamboo-shaped boron nitride nanotube hierarchical structure with ultrathin boron nitride nanosheets loaded on the surface comprises the following steps:
2.00g of ammonium pentaborate, 3.09g of ammonia borane complex and 1.60g of magnesium oxide are weighed (molar ratio is 1:10: 4). Firstly, uniformly mixing raw materials, pouring the mixture into a stainless steel ball milling tank and vacuumizing; cooling after ball milling for 6h, and taking out a coarse grinding product; uniformly spreading the ball-milled product on the bottom of an alumina ceramic boat, and covering an alumina substrate on the upper end of the ceramic boat; then putting the ceramic boat into a tube furnace, adjusting the temperature rise rate of the tube furnace to 10 ℃/min, raising the temperature to 1250 ℃ in a flowing ammonia atmosphere, preserving the temperature for 10h, and then automatically cooling; taking out the alumina substrate loaded with the white flocculent product, and placing the alumina substrate in absolute ethyl alcohol for ultrasonic treatment for 60min to obtain a boron nitride suspension; and adding 80ml of 5mol/L hydrochloric acid into the suspension, then carrying out hot stirring at 80 ℃ for 24h, filtering, washing with absolute ethyl alcohol, and finally drying under the vacuum condition of 80 ℃ for 24h to obtain the hierarchical structure powder of the bamboo-shaped boron nitride nanotube with the surface loaded with the ultrathin nanosheets.
The product is analyzed by XRD, FSEM and TEM/HRTEM, the yield of the bamboo-shaped boron nitride nanotube hierarchical structure sample with the ultrathin nanosheets loaded on the surface is more than 93%, the diameter range is 0.4-1.2 mu m, the interior of the nanotube is in a periodic bamboo-shaped structure, the inner diameter range is 50-200nm, the average inner diameter is 80nm, and the maximum tube length of the sample is more than 8 mu m; a large number of ultrathin hBN nano sheets are loaded outside, and the thickness of the sheet layer ranges from 10nm to 15 nm.
Claims (6)
1. A preparation method of a bamboo-shaped boron nitride nanotube hierarchical structure with ultrathin boron nitride nanosheets loaded on the surface is characterized in that ammonium pentaborate, ammonia borane complex and magnesium oxide are used as raw materials; firstly, uniformly mixing raw materials according to a molar ratio, pouring the obtained mixture into a stainless steel ball milling tank, vacuumizing, carrying out ball milling for a period of time, cooling, taking out a coarse grinding product, uniformly paving the ball milling product at the bottom of an alumina ceramic boat, covering an alumina substrate on the upper end of the ceramic boat, then putting the ceramic boat into a tube furnace, adjusting the temperature rise rate of the tube furnace to 10 ℃/min, raising the temperature to 1000-1250 ℃ in a flowing ammonia atmosphere, carrying out heat preservation for a period of time, then automatically cooling, taking out a white flocculent product loaded on the alumina substrate, and purifying to obtain a powder with a hierarchical structure of bamboo-shaped boron nitride nanotubes and ultrathin nano sheets loaded on the surface;
the molar ratio NH of the ammonium borate to the ammonia borane complex to the magnesium oxide4B5O8：NH3BH3: MgO is 1: (6-10): (1-4).
2. The surface-supported ultra-thin nitride of claim 1The preparation method of the bamboo-shaped boron nitride nanotube hierarchical structure of the boron nanosheet is characterized in that the ball milling process is carried out by performing a ball milling process on the boron nanosheet at a revolution ratio of 50-100 rpm, wherein the revolution ratio and the rotation ratio are 1: 2, the ball milling pot and the ball milling material are ZrO2The ball milling time is 3-6 h.
3. The preparation method of the bamboo-like boron nitride nanotube hierarchical structure with the surface loaded with the ultrathin boron nitride nanosheets, according to claim 1, is characterized in that the heat preservation time is 3-10h, and the flow rate of ammonia gas is 0.3-1L/min.
4. The preparation method of the bamboo-like boron nitride nanotube hierarchical structure with the surface loaded with the ultrathin boron nitride nanosheets according to claim 1, wherein the white flocculent product collection process is as follows: and (3) placing the alumina substrate loaded with the white flocculent product in absolute ethyl alcohol for 30-60min by ultrasonic treatment to obtain the boron nitride suspension.
5. The preparation method of the bamboo-like boron nitride nanotube hierarchical structure with the surface loaded with the ultrathin boron nitride nanosheets according to claim 4, wherein the purification process of the white flocculent product is as follows: adding 5mol/L hydrochloric acid into the boron nitride suspension, then carrying out hot stirring at 80 ℃ for 6-24h, filtering, washing with alcohol, and finally drying under the vacuum condition of 80 ℃ for 10-24h to obtain the bamboo-shaped boron nitride nanotube hierarchical structure powder with the ultrathin nanosheets loaded on the surface.
6. The method for preparing the hierarchical structure of the bamboo-shaped boron nitride nanotube with the ultrathin boron nitride nanosheets loaded on the surface of the hierarchical structure of the bamboo-shaped boron nitride nanotube, according to claim 1, is characterized in that the pipe diameter range of the hierarchical structure of the bamboo-shaped boron nitride nanotube with the ultrathin nanosheets loaded on the surface of the hierarchical structure of the bamboo-shaped boron nitride nanotube is 0.2-1 μm, the length of the hierarchical structure of the bamboo-shaped boron nitride nanotube is greater than 5 μm, the interior of the nanotube is in a periodic bamboo-shaped structure, a large number of ultrathin hBN nanosheets are loaded on the exterior of the hierarchical structure of the bamboo-shaped boron nitride nanotube, the average thickness of the nanosheets is 13nm, and the thickness range of the whole boron nitride nanosheets is 50-250 nm.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810216476.7A CN108483413B (en) | 2018-03-16 | 2018-03-16 | Preparation method of bamboo-shaped boron nitride nanotube hierarchical structure with ultrathin boron nitride nanosheets loaded on surface |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810216476.7A CN108483413B (en) | 2018-03-16 | 2018-03-16 | Preparation method of bamboo-shaped boron nitride nanotube hierarchical structure with ultrathin boron nitride nanosheets loaded on surface |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN108483413A CN108483413A (en) | 2018-09-04 |
| CN108483413B true CN108483413B (en) | 2021-09-10 |
Family
ID=63339280
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810216476.7A Active CN108483413B (en) | 2018-03-16 | 2018-03-16 | Preparation method of bamboo-shaped boron nitride nanotube hierarchical structure with ultrathin boron nitride nanosheets loaded on surface |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN108483413B (en) |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110642234A (en) * | 2019-11-13 | 2020-01-03 | 成都理工大学 | Preparation method of nano whisker-shaped boron nitride oxide |
| CN110817814B (en) * | 2019-12-06 | 2022-08-16 | 桂林理工大学 | Preparation method and product of thin-wall BN micro-tube with one-dimensional hierarchical structure |
| RU2742643C1 (en) * | 2020-11-10 | 2021-02-09 | Акционерное общество «ЦТК-ЕВРО» | Use of a suspension of hexagonal boron nitride to increase the heat flux passing through structural elements exposed to uneven heating by an external source |
| CN114538390B (en) * | 2022-02-16 | 2023-06-23 | 桂林理工大学 | Boron nitride hollow tube with lamellar directional coverage forming tube wall and preparation method thereof |
| CN115160023B (en) * | 2022-08-03 | 2022-12-27 | 中国人民解放军火箭军工程大学 | Method for preparing boron nitride nano material on porous ceramic pore surface |
| CN117285015B (en) * | 2023-11-24 | 2024-01-26 | 上海硼矩新材料科技有限公司 | Device and production method for preparing BNTs based on ammonia borane decomposer |
| CN117865721B (en) * | 2024-03-08 | 2024-05-07 | 中国北方发动机研究所(天津) | Preparation method of in-situ grown superfine boron nitride nanotube |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1854065A (en) * | 2005-04-20 | 2006-11-01 | 中国科学院金属研究所 | Production of boron nitride nanometer tube with water as growth improver |
| CN103043633A (en) * | 2013-01-09 | 2013-04-17 | 广西大学 | Method for preparing hexagonal boron nitride nano composite structure |
| CN103964403A (en) * | 2014-04-08 | 2014-08-06 | 南京航空航天大学 | Preparation method of three-dimensional porous hexagonal boron nitride |
| CN104386657A (en) * | 2014-11-12 | 2015-03-04 | 河北工业大学 | Preparation method of high-crystallinity boron nitride |
| CN107161961A (en) * | 2017-06-30 | 2017-09-15 | 武汉理工大学 | A kind of sea urchin shape boron nitride nanosheet nanotube hierarchy and preparation method thereof |
-
2018
- 2018-03-16 CN CN201810216476.7A patent/CN108483413B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1854065A (en) * | 2005-04-20 | 2006-11-01 | 中国科学院金属研究所 | Production of boron nitride nanometer tube with water as growth improver |
| CN103043633A (en) * | 2013-01-09 | 2013-04-17 | 广西大学 | Method for preparing hexagonal boron nitride nano composite structure |
| CN103964403A (en) * | 2014-04-08 | 2014-08-06 | 南京航空航天大学 | Preparation method of three-dimensional porous hexagonal boron nitride |
| CN104386657A (en) * | 2014-11-12 | 2015-03-04 | 河北工业大学 | Preparation method of high-crystallinity boron nitride |
| CN107161961A (en) * | 2017-06-30 | 2017-09-15 | 武汉理工大学 | A kind of sea urchin shape boron nitride nanosheet nanotube hierarchy and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| Formation and Atomic Structure of Hierarchical Boron Nitride Nanostructures;R. A. Silva-Molina et al.;《J. Phys. Chem. C》;20151023;第119卷;第25576-25584页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN108483413A (en) | 2018-09-04 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN108483413B (en) | Preparation method of bamboo-shaped boron nitride nanotube hierarchical structure with ultrathin boron nitride nanosheets loaded on surface | |
| Wu et al. | In-situ construction of coral-like porous P-doped g-C3N4 tubes with hybrid 1D/2D architecture and high efficient photocatalytic hydrogen evolution | |
| Peng et al. | A hydrothermal etching route to synthesis of 2D MXene (Ti3C2, Nb2C): Enhanced exfoliation and improved adsorption performance | |
| Song et al. | From layered basic zinc acetate nanobelts to hierarchical zinc oxide nanostructures and porous zinc oxide nanobelts | |
| Li et al. | Hydrothermal synthesis and characterization of TiO2 nanorod arrays on glass substrates | |
| Xu et al. | Synthesis, properties and applications of nanoscale nitrides, borides and carbides | |
| CN108545708B (en) | Preparation method of coralline hexagonal boron nitride micro-nano tube sheet composite structure | |
| Tang et al. | Sol–solvothermal synthesis and microwave evolution of La (OH) 3 nanorods to La2O3 nanorods | |
| Fang et al. | Temperature-controlled growth of α-Al 2 O 3 nanobelts and nanosheets | |
| Shi et al. | Controlled fabrication of SnO 2 arrays of well-aligned nanotubes and nanowires | |
| Wang et al. | Facile synthesis of hematite nanoparticles and nanocubes and their shape-dependent optical properties | |
| CN103922295B (en) | A kind of preparation method of boron nitride nano-tube | |
| Liu et al. | Fabrication and photoluminescence properties of hollow Gd 2 O 3: Ln (Ln= Eu3+, Sm3+) spheres via a sacrificial template method | |
| An et al. | Preparation of porous chromium oxide nanotubes using carbon nanotubes as templates and their application as an ethanol sensor | |
| CN110980664B (en) | Porous few-layer h-BN nanosheet and preparation method thereof | |
| CN101348242A (en) | Method for preparing boron nitride nanotube by magnesium reduction | |
| Li et al. | Synthesis and mechanism of single-crystalline β-SiC nanowire arrays on a 6H-SiC substrate | |
| Yu et al. | Preparation and piezoelectric catalytic performance of flexible inorganic Ba 1− x Ca x TiO 3 via electrospinning | |
| Guo et al. | Preparation of SiC nanowires with fins by chemical vapor deposition | |
| Shi et al. | NiO nanotubes assembled in pores of porous anodic alumina and their optical absorption properties | |
| Wang et al. | Growth mechanism and ultraviolet-visible property of novel thick-walled boron nitride nanostructures | |
| Liu et al. | Facile growth of oriented SiC nanowires arrays on carbon fiber cloth via CVD | |
| CN101811677B (en) | Method for preparing hollow porous quadruped titanium nitride | |
| CN110817814B (en) | Preparation method and product of thin-wall BN micro-tube with one-dimensional hierarchical structure | |
| Zheng et al. | Synthesis and characterization of boron nitride sponges as a novel support for metal nanoparticles |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |