CN114538390A - Boron nitride hollow tube with tube wall formed by directionally covering lamellar and preparation method thereof - Google Patents
Boron nitride hollow tube with tube wall formed by directionally covering lamellar and preparation method thereof Download PDFInfo
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Abstract
The invention relates to a boron nitride hollow tube with a tube wall formed by directionally covering a lamellar, which mainly comprises the following steps: taking ammonia water, boric acid and magnesium nitrate as raw materials, and carrying out hydrothermal reaction to obtain a boron-containing precursor; then, calcining the boron-containing precursor in a nitrogen-containing atmosphere to obtain a nitriding product; and then, mixing the nitridation product with ammonium chloride, and putting the mixture into a high-pressure reaction kettle for reaction to obtain the hollow boron nitride. The invention firstly prepares the boron nitride hollow tube with the tube wall formed by directionally covering the lamellar by using the boron-containing precursor through high-temperature nitridation and high-pressure synthesis process.
Description
Technical Field
The invention belongs to the field of inorganic materials, and particularly relates to a boron nitride hollow tube with a tube wall formed by directionally covering a lamellar layer and a preparation method thereof.
Background
Boron Nitride (BN), which is called "white graphite" has a structure similar to that of graphite, but has more excellent physicochemical properties than graphite, such as high heat resistance and thermal conductivity, excellent dielectric properties (good high-temperature insulation), good high-temperature stability, low thermal expansion coefficient, good lubricity and chemical stability (excellent corrosion resistance), and the like. In recent years, with the rapid development of materials, materials have been developed from zero-dimensional, one-dimensional, two-dimensional, and the like structures to multi-dimensional structures. According to the difference of dimension, appearance and size, the boron nitride material comprises a nano tube, a micro tube, a nano belt, a micro belt, a nano sheet, a micro sheet and the like. The controllable preparation of boron nitride micron and nanometer materials with different dimensions, shapes and sizes is a hotspot of current subject research, and with the deep research of boron nitride materials, the boron nitride micron and nanometer materials are widely applied to the aspects of strengthening and toughening of ceramic materials, adsorption of heavy metal ions and organic dyes, improvement of the heat conductivity of polymers and the like.
At present, various methods are available for preparing boron nitride with different structures, such as a ball milling method, a high-pressure benzene heating method, a vapor deposition method and the like, ammonia pentaborate, an ammonia borane complex and magnesium oxide are used as raw materials, such as Jiyu pure, the raw materials are uniformly ball-milled, ammonia gas is introduced for protection for 6 hours, and a BN nanotube-nanosheet hierarchical structure is obtained, wherein the length of the BN nanotube-nanosheet hierarchical structure is greater than 5 microns, the middle part of the BN nanotube-nanosheet hierarchical structure is a bamboo-shaped hollow structure, the inner pipe diameter is 50-350 nm, and the outer diameter range is 200-800 nm. The UV-Vis and PL spectrum results show that the BN nanotube-nanosheet hierarchical structure has certain application potential in the field of ultraviolet light materials. However, this method is not suitable for mass production because of its low yield. The preparation method comprises the steps of taking boric acid and magnesium chloride as reaction raw materials for Liu-Bian and the like, taking sodium chloride or potassium chloride as a cosolvent, mixing according to a certain proportion, annealing at 800-1000 ℃ to form a boron-containing precursor, then introducing ammonia gas for protection, annealing at about 1100 ℃, and collecting a thin-wall BN micro-tube with a one-dimensional hierarchical structure, wherein the inner tube diameter range is 0.4-2 um, the tube length is 5-60 um, the tube wall thickness is 30-100 nm, boron nitride nano-thin sheets are loaded on the tube surface, the thin-wall BN micro-tubes are interwoven to form boron nitride sheet layers, and the thickness of the boron nitride sheet layers is 40-80 nm.
Disclosure of Invention
The invention aims to solve the technical problem of providing a boron nitride hollow tube with a tube wall formed by directionally covering a lamellar layer and a preparation method thereof aiming at the defects in the prior art. According to the invention, ammonia water, boric acid and magnesium nitrate are used as raw materials for hydrothermal reaction to obtain a boron-containing precursor, and a boron nitride hollow tube with a tube wall formed by directionally covering a lamellar layer is prepared by a two-step synthesis process combining high-temperature nitridation and high-pressure reaction.
The technical scheme adopted by the invention for solving the problems is as follows:
a method for preparing a boron nitride hollow tube with a tube wall formed by directionally covering a sheet layer comprises the following main steps:
(1) mixing boric acid and magnesium nitrate in water, and then adding ammonia water to adjust the pH value to 10-10.5 to obtain a precursor solution; then, carrying out hydrothermal reaction on the precursor solution to obtain a boron-containing precursor;
(2) calcining the boron-containing precursor in a nitrogen-containing atmosphere to obtain a nitriding product;
(3) and mixing the nitridation product with ammonium chloride, and putting the mixture into a high-pressure reaction kettle for reaction to obtain the hollow boron nitride with the tube wall having a lamellar structure.
According to the scheme, in the step (1), the molar ratio of boric acid to magnesium nitrate is 3: 2-1; the concentration of the ammonia water is 25-40%.
According to the scheme, in the step (1), boric acid and magnesium nitrate are mixed and dissolved in water, and the concentration of the boric acid is controlled to be 2-4 mol/L, and the concentration of the magnesium nitrate is controlled to be 1-3 mol/L.
According to the scheme, in the step (1), the hydrothermal reaction time is 20-30 h, and the temperature is 180-250 ℃.
According to the scheme, in the step (2), the nitrogen-containing atmosphere is NH3The flow rate of the nitrogen-containing atmosphere is 100 ml/min-200 ml/min, and the optimal atmosphere flow rate is 100 ml/min.
According to the scheme, in the step (2), the calcining temperature is 850-1000 ℃, and the calcining heat preservation time is 30-60 min.
According to the scheme, in the step (3), the mass ratio of the nitridation product to the ammonium chloride is 1: 1-2 mixing.
According to the scheme, in the step (3), the reaction time in the high-pressure reaction kettle is 1-2 hours, and the reaction temperature is 500-600 ℃.
The boron nitride hollow tube material with the tube wall having the lamella (fish scale) structure is obtained by the preparation method, the lamella are regularly and directionally arranged along the tube diameter direction to form the tube wall with the scale-like structure, the thickness of the lamella is 10-20 nm, the number of the lamella layers is 1-3, the inner diameter range of the hollow tube is 0.2-1.2 mu m, the length of the tube is 0.6-2 mu m, and the thickness of the tube wall is 10-100 nm.
The following chemical reactions may occur in the boron nitride hollow tube during the synthesis process:
Mg(NO3)2(l)+H3BO3(l)+NH3 .H2O(l)→MgBO2(OH)(s)+NH4NO3(l)+H2O(l) (1)
MgBO2(OH)(s)+NH3(g)→[B-Mg-O-N-H](s) (2)
[B-Mg-O-N-H](s)+NH4Cl(s)→BNMTs-BNnanoplates(BNMT-BNNPs)(s)+MgCl2(l)+H2(g)+H2O(l) (3)
the possible reaction mechanism of the above synthesis process is: boron source is from solid MgBO2(OH) precursor, MgBO with gradual temperature rise during nitridation2The (OH) precursor gradually changes into liquid state, part of boron element is precipitated from the surface of the precursor to form gaseous boron oxide, and the internal boron element continuously diffuses outwards due to concentration difference to form MgBO2(OH) precursor as template reacts with external nitrogen active gas to form boron nitride micron tube shell, boron-containing coated BN shellThe precursor and ammonium chloride are decomposed at high temperature and high pressure in a high-pressure reaction kettle to form active N and NH3And H2The mixed gas reacts to form an inner BN layer. Meanwhile, the active gaseous substance not only reacts with the precursor B, but also can erode the surface layer of the tube under the special condition of closed self-generation high pressure, so that defects such as holes, fragments and the like are formed in a layer with a certain BN thickness, but the generated holes and fragments are still regularly arranged along the axial direction of the tube diameter, and thus a few-layer scaly hollow boron nitride structure with regular axial arrangement is finally formed.
Compared with the prior art, the invention has the beneficial effects that:
1. the invention uses simple and easily obtained boric acid, ammonia water and magnesium nitrate as raw materials to prepare a boron-containing precursor, the precursor is used as a boron source to carry out preliminary nitridation reaction in a tubular furnace, and then the precursor and ammonium chloride are subjected to high-temperature and high-pressure reaction to prepare the boron nitride hollow tube with the sheet layer directionally covered and formed on the tube wall, the purity of the product reaches 99%, and the method is favorable for large-scale industrialized preparation.
2. The few-layer scaly hollow boron nitride structure with regular axial arrangement prepared by the invention is formed by self-assembling nano sheets, documents do not report, the specific surface area of the product is greatly improved by the special morphology, and the specific surface area can reach 272.6m2g-1Is obviously higher than the specific surface area (25 m) of boron nitride powder on the market2g-1) Has good potential application prospect in the fields of gas adsorption, water pollution treatment, electrochemistry, hydrogen storage, drug carriers and the like.
Drawings
Fig. 1 is a Scanning Electron Microscope (SEM) spectrum of the BN sample obtained in comparative example 1.
Fig. 2 is a Scanning Electron Microscope (SEM) spectrum of the BN sample obtained in example 1.
Fig. 3 is a Transmission Electron Microscope (TEM) photograph of the BN sample obtained in example 1.
Fig. 4 is an X-ray diffraction (XRD) pattern of the BN sample obtained in example 1.
Fig. 5 is an infrared (FTIR) spectrum of the BN sample obtained in example 1.
Fig. 6 is a nitrogen adsorption-desorption isotherm map of the BN sample obtained in example 1.
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.
In the following examples, the morphology of the resulting product was observed with a FEI Quanta FEG model 250 scanning electron microscope (FSEM); researching the internal microstructure of the sample by using a JEM2100-F type Transmission Electron Microscope (TEM), ultrasonically dispersing the product in absolute ethyl alcohol, and dropwise adding the product onto a carbon film; x-ray diffraction analysis (XRD) Using an X-ray powder diffractometer model Rigaku D/MAX-LLIA
2 theta is 10-80 degrees; infrared spectroscopy (FTIR) test using Thermo Nexus470 fourier transform infrared spectrometer (thermoelectric high force corporation, usa); specific surface area (BET) testing Using a TriStar model II 3200 analyzer.
Comparative example 1
(1) Under magnetic stirring at room temperature, H is added3BO3And Mg (NO)3)2Mixing and dissolving in deionized water to make the concentration respectively 3mol/L and 2mol/L, and then dropwise adding ammonia water with the concentration of 25% until the pH value is 10 to obtain a precursor solution. Then, taking 80ml of precursor solution, putting the precursor solution into a hydrothermal reaction kettle with a polytetrafluoroethylene lining and a capacity of 100ml, heating to 200 ℃, keeping the temperature for 20 hours under an isothermal condition, naturally cooling to room temperature, filtering a product, washing the product with deionized water for three times, and performing vacuum drying at 110 ℃ for 12 hours to obtain a boron-containing precursor;
(2) putting the prepared boron-containing precursor into a tube furnace, vacuumizing, introducing ammonia gas with the flow rate of 150ml/min, preserving the temperature at 1000 ℃ for 30min, cooling to 200 ℃ along with the furnace, closing a vent valve, and naturally cooling to room temperature to obtain a nitriding product;
(3) and dispersing the nitrided product in 20ml of distilled water, adding 30ml of 12mol/L hydrochloric acid, heating and stirring for 5h at 50 ℃, washing and centrifuging for three times by using deionized water, washing for two times by using ethanol, and finally drying in vacuum for 10h at 50 ℃ to obtain a low-crystallinity boron nitride tubular object with no surface covered by boron nitride nanosheets, which is recorded as a BN sample.
As shown in fig. 1, the SEM spectrum of the BN sample prepared in this comparative example. The photo shows that the BN sample is a low-crystallinity boron nitride tubular object with no boron nitride nanosheet covered on the surface, the inner tube diameter is 0.1-0.3 mu m, the tube length is 0.3-1 mu m, the tube wall thickness is 10-100 nm, and the surface is not covered with the boron nitride nanosheet.
Example 1
A method for preparing a boron nitride hollow tube with a tube wall formed by directionally covering a lamellar comprises the following steps:
(1) under magnetic stirring at room temperature, H is added3BO3And Mg (NO)3)2Mixing and dissolving in deionized water to make the concentration respectively 3mol/L and 2mol/L, and then dropwise adding ammonia water with the concentration of 25% until the pH value is 10 to obtain a precursor solution. Then, taking 80ml of precursor solution, putting the precursor solution into a hydrothermal reaction kettle with a polytetrafluoroethylene lining and a capacity of 100ml, heating to 200 ℃, keeping the temperature for 20 hours under an isothermal condition, naturally cooling to room temperature, filtering a product, washing the product with deionized water for three times, and performing vacuum drying at 110 ℃ for 12 hours to obtain a boron-containing precursor;
(2) putting the prepared boron-containing precursor into a tube furnace, vacuumizing, introducing ammonia gas with the flow of 100ml/min, preserving the temperature at 1000 ℃ for 30min, cooling to 200 ℃ along with the furnace, closing a vent valve, and naturally cooling to room temperature to obtain a nitriding product;
(3) mixing the nitridation product with ammonium chloride according to the mass ratio of 1: 1, mixing and putting the mixture into a high-pressure reaction kettle for reaction for 1 hour at the reaction temperature of 500 ℃ to obtain a crude product; dispersing the crude product in 20ml of distilled water, adding 30ml of 12mol/L hydrochloric acid, heating and stirring for 5h at 50 ℃, then washing and centrifuging for three times by using deionized water, washing twice by using ethanol, and finally drying in vacuum for 10h at 50 ℃ to obtain a boron nitride hollow tube with a tube wall having a lamellar (fish scale-like) structure, wherein the boron nitride hollow tube is recorded as a BN sample.
As shown in fig. 2, the SEM spectrum of the BN sample prepared in this example. The photo shows that the BN sample is in a boron nitride hollow tube structure, the inner tube diameter range is 0.2-1.2 mu m, the tube length is 0.6-1 mu m, the tube wall thickness is 10-100 nm, the lamella layers are regularly and directionally arranged along the tube diameter direction to form a tube wall with a scale-like structure, the lamella thickness is 10-20 nm, and the number of the boron nitride layers is 1-3.
As shown in fig. 3, HRTEM of the BN sample prepared in this example was taken. From the photographs, clear lattice fringes were observed with a lattice spacing of about 0.34nm, which is consistent with the lattice constant of the (002) crystal plane of h-BN, indicating that the h-BN material.
As shown in fig. 4, the XRD spectrum of the BN sample prepared in this example has 5 distinct main diffraction peaks located at 2 θ ═ 26.76 °, 41.60 °, 50.14 °, 55.16 °, and 75.93 °, respectively, and the peaks correspond to (002), (100), (102), (004), and (110) crystal planes of the h-BN crystal (JCPDF No.34-0421), which indicates that the sample has no impurity phase and the purity is higher than 99%.
As shown in FIG. 5, the FTIR spectrum of the BN sample prepared in this example shows that there are 3 distinct characteristic absorption peaks in the spectrum, which are located at 811, 1373 and 3411cm respectively-1To (3). Wherein, 1373 and 811cm-1The absorption peaks at (A) correspond to the in-plane stretching vibration and the out-of-plane bending vibration of the B-N bond in the h-BN material respectively, and 3411cm-1The absorption peak at (A) is usually due to the absorption of water or stretching vibration of O-H bonds in the slight oxidation of the surface.
As shown in FIG. 6, the nitrogen adsorption-desorption isotherm of the BN sample prepared in this example was found to belong to the type IV adsorption/desorption isotherm having a hysteresis loop of type H3, and when the relative pressure was close to 1.0, N was found to be present2The adsorption quantity of (2) is obviously increased, the pore diameter of the sample contains macropores, and the specific surface area of the sample is calculated to be 272.6m2g-1。
Example 2
A method for preparing a boron nitride hollow tube with a tube wall formed by directionally covering a lamellar comprises the following steps:
(1) under magnetic stirring at room temperature, H is added3BO3And Mg (NO)3)2Mixing and dissolving in deionized water to make the concentration respectively be 3mol/L and2mol/L, then dropwise adding ammonia water with the concentration of 25% until the pH value is 10, and obtaining a precursor solution. Then, taking 80ml of precursor solution, putting the precursor solution into a hydrothermal reaction kettle with a polytetrafluoroethylene lining and a capacity of 100ml, heating to 200 ℃, keeping the temperature for 20 hours under an isothermal condition, naturally cooling to room temperature, filtering a product, washing the product with deionized water for three times, and performing vacuum drying at 110 ℃ for 12 hours to obtain a boron-containing precursor;
(2) putting the prepared boron-containing precursor into a tube furnace, vacuumizing, introducing ammonia gas with the flow rate of 150ml/min, preserving the temperature at 1000 ℃ for 30min, cooling to 200 ℃ along with the furnace, closing a vent valve, and naturally cooling to room temperature to obtain a nitriding product;
(3) mixing the nitridation product with ammonium chloride according to the mass ratio of 1: 1, mixing and putting the mixture into a high-pressure reaction kettle for reaction for 1 hour at the reaction temperature of 500 ℃ to obtain a crude product; dispersing the crude product in 20ml of distilled water, adding 30ml of 12mol/L hydrochloric acid, heating and stirring for 5h at 50 ℃, then washing and centrifuging for three times by using deionized water, washing twice by using ethanol, and finally drying in vacuum for 10h at 50 ℃ to obtain a boron nitride hollow tube with a tube wall having a lamellar (fish scale-like) structure, wherein the boron nitride hollow tube is recorded as a BN sample.
Example 3
A method for preparing a boron nitride hollow tube with a tube wall formed by directionally covering a lamellar comprises the following steps:
(1) under magnetic stirring at room temperature, H is added3BO3And Mg (NO)3)2Mixing and dissolving in deionized water to make the concentrations respectively be 3mol/L and 2mol/L, and then dropwise adding ammonia water with the concentration of 25% until the pH value is 10 to obtain a precursor solution. Then, taking 80ml of precursor solution, putting the precursor solution into a hydrothermal reaction kettle with a polytetrafluoroethylene lining and a capacity of 100ml, heating to 200 ℃, keeping the temperature for 20 hours under an isothermal condition, naturally cooling to room temperature, filtering a product, washing the product with deionized water for three times, and performing vacuum drying at 110 ℃ for 12 hours to obtain a boron-containing precursor;
(2) putting the prepared boron-containing precursor into a tube furnace, vacuumizing, introducing ammonia gas with the flow of 200ml/min, preserving the temperature at 1000 ℃ for 30min, cooling to 200 ℃ along with the furnace, closing a vent valve, and naturally cooling to room temperature to obtain a nitriding product;
(3) mixing the nitridation product with ammonium chloride according to the mass ratio of 1: 1, mixing and putting the mixture into a high-pressure reaction kettle for reaction for 1 hour at the reaction temperature of 500 ℃ to obtain a crude product; dispersing the crude product in 20ml of distilled water, adding 30ml of 12mol/L hydrochloric acid, heating and stirring for 5h at 50 ℃, then washing and centrifuging for three times by using deionized water, washing twice by using ethanol, and finally drying in vacuum for 10h at 50 ℃ to obtain a boron nitride hollow tube with a tube wall having a lamellar (fish scale-like) structure, wherein the boron nitride hollow tube is recorded as a BN sample.
Example 4
A method for preparing a boron nitride hollow tube with a tube wall formed by directionally covering a sheet layer comprises the following steps:
(1) under magnetic stirring at room temperature, H is added3BO3And Mg (NO)3)2Mixing and dissolving in deionized water to make the concentration respectively 3mol/L and 2mol/L, and then dropwise adding ammonia water with the concentration of 25% until the pH value is 10 to obtain a precursor solution. Then, taking 80ml of precursor solution, putting the precursor solution into a hydrothermal reaction kettle with a polytetrafluoroethylene lining and a capacity of 100ml, heating to 200 ℃, keeping the temperature for 20 hours under an isothermal condition, naturally cooling to room temperature, filtering a product, washing the product with deionized water for three times, and performing vacuum drying at 110 ℃ for 12 hours to obtain a boron-containing precursor;
(2) putting the prepared boron-containing precursor into a tube furnace, vacuumizing, introducing ammonia gas with the flow of 100ml/min, preserving the heat at 850 ℃ for 1h, cooling to 200 ℃ along with the furnace, closing a vent valve, and naturally cooling to room temperature to obtain a nitriding product;
(3) mixing the nitridation product with ammonium chloride according to the mass ratio of 1: 1, mixing and putting the mixture into a high-pressure reaction kettle for reaction for 1 hour at the reaction temperature of 500 ℃ to obtain a crude product; dispersing the crude product in 20ml of distilled water, adding 30ml of 12mol/L hydrochloric acid, heating and stirring for 5h at 50 ℃, then washing and centrifuging for three times by using deionized water, washing twice by using ethanol, and finally drying in vacuum for 10h at 50 ℃ to obtain a boron nitride hollow tube with a tube wall having a lamellar (fish scale-like) structure, wherein the boron nitride hollow tube is recorded as a BN sample.
Example 5
A method for preparing a boron nitride hollow tube with a tube wall formed by directionally covering a lamellar comprises the following steps:
(1) under magnetic stirring at room temperature, H is added3BO3And Mg (NO)3)2Mixing and dissolving in deionized water to make the concentration respectively 3mol/L and 2mol/L, and then dropwise adding ammonia water with the concentration of 25% until the pH value is 10 to obtain a precursor solution. Then, taking 80ml of precursor solution, putting the precursor solution into a hydrothermal reaction kettle with a polytetrafluoroethylene lining and the capacity of 100ml, heating to 200 ℃, keeping the temperature for 20 hours under an isothermal condition, naturally cooling to room temperature, filtering a product, washing the product with deionized water for three times, and performing vacuum drying for 12 hours at 110 ℃ to obtain a boron-containing precursor;
(2) putting the prepared boron-containing precursor into a tube furnace, vacuumizing, introducing ammonia gas with the flow of 100ml/min, preserving the heat at 900 ℃ for 1h, cooling to 200 ℃ along with the furnace, closing a vent valve, and naturally cooling to room temperature to obtain a nitriding product;
(3) mixing the nitridation product with ammonium chloride according to the mass ratio of 1: 1, mixing and putting the mixture into a high-pressure reaction kettle for reaction for 1 hour at the reaction temperature of 500 ℃ to obtain a crude product; dispersing the crude product in 20ml of distilled water, adding 30ml of 12mol/L hydrochloric acid, heating and stirring for 5h at 50 ℃, then washing and centrifuging for three times by using deionized water, washing twice by using ethanol, and finally drying in vacuum for 10h at 50 ℃ to obtain a boron nitride hollow tube with a tube wall having a lamellar (fish scale-like) structure, wherein the boron nitride hollow tube is recorded as a BN sample.
The above description is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, many modifications and changes can be made without departing from the inventive concept of the present invention, and these modifications and changes are within the protection scope of the present invention.
Claims (9)
1. A boron nitride hollow tube with a tube wall formed by directionally covering lamellar layers is characterized in that the lamellar layers are directionally arranged along the tube diameter direction to form the tube wall, the number of the lamellar layers is 1-3, the thickness of the lamellar layers is 10-20 nm, the inner diameter range of the hollow tube is 0.2-1.2 mu m, the length of the tube is 0.6-2 mu m, and the thickness of the tube wall is 10-100 nm.
2. A preparation method of a boron nitride hollow tube with a tube wall formed by directionally covering a lamellar is characterized by mainly comprising the following steps:
(1) mixing boric acid and magnesium nitrate, dissolving in water, and then adding ammonia water to adjust the pH value to 10-10.5 to obtain a precursor solution; carrying out hydrothermal reaction on the precursor solution to obtain a boron-containing precursor;
(2) calcining the boron-containing precursor in a nitrogen-containing atmosphere to obtain a nitriding product;
(3) and mixing the nitridation product with ammonium chloride, and putting the mixture into a high-pressure reaction kettle for reaction to obtain the hollow boron nitride with the tube wall having a lamellar structure.
3. The method for preparing the boron nitride hollow tube with the oriented coverage of the sheet layer to form the tube wall according to the claim 2, wherein in the step (1), the molar ratio of boric acid to magnesium nitrate is 3: 2 to 1.
4. The method for preparing the boron nitride hollow tube with the oriented and formed tube wall covered with the laminar layer according to claim 2, wherein in the step (1), boric acid and magnesium nitrate are mixed and dissolved in water, and the concentration of the boric acid is controlled to be 2-4 mol/L and the concentration of the magnesium nitrate is controlled to be 1-3 mol/L.
5. The method for preparing the boron nitride hollow tube with the sheet layer directionally covered and formed on the tube wall according to claim 2, wherein in the step (1), the hydrothermal reaction time is 20-30 h, and the temperature is 180-250 ℃.
6. The method for preparing boron nitride hollow tube with directionally covered and formed tube wall in lamellar layer according to claim 2, wherein in the step (2), the nitrogen-containing atmosphere is NH3The flow rate of the atmosphere is 100 ml/min-200 ml/min.
7. The method for preparing the boron nitride hollow tube with the tube wall formed by directionally covering the lamellar layer according to claim 2, wherein in the step (2), the calcining temperature is 850-1000 ℃, and the heat preservation time is 30-60 min.
8. The method for preparing the boron nitride hollow tube with the oriented coverage of the sheet layer to form the tube wall according to claim 2, wherein in the step (3), the mass ratio of the nitridation product to the ammonium chloride is 1: 1-2 mixing.
9. The method for preparing the boron nitride hollow tube with the oriented laminar covering for forming the tube wall according to claim 2, wherein in the step (3), the reaction time in the high-pressure reaction kettle is 1-2 hours, and the reaction temperature is 500-600 ℃.
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