CN114538390B - Boron nitride hollow tube with lamellar directional coverage forming tube wall and preparation method thereof - Google Patents

Boron nitride hollow tube with lamellar directional coverage forming tube wall and preparation method thereof Download PDF

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CN114538390B
CN114538390B CN202210140906.8A CN202210140906A CN114538390B CN 114538390 B CN114538390 B CN 114538390B CN 202210140906 A CN202210140906 A CN 202210140906A CN 114538390 B CN114538390 B CN 114538390B
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boron nitride
lamellar
tube
tube wall
hollow tube
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CN114538390A (en
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王吉林
李正德
吉钰纯
陈文卓
宣伟萍
顾远平
周美均
郑国源
龙飞
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Guilin University of Technology
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Abstract

The invention relates to a boron nitride hollow tube with a lamellar directional coverage formed tube wall, which is prepared by the following main processes: 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 nitriding product with ammonium chloride, and placing the mixture into a high-pressure reaction kettle for reaction to obtain the boron nitride with the hollow structure. The invention prepares the boron nitride hollow tube with the lamellar directional coverage forming the tube wall by a synthesis process of high temperature nitridation and high pressure after high temperature nitridation of a boron-containing precursor for the first time.

Description

Boron nitride hollow tube with lamellar directional coverage forming tube wall and preparation method thereof
Technical Field
The invention belongs to the field of inorganic materials, and particularly relates to a boron nitride hollow tube with a lamellar directional coverage formed tube wall and a preparation method thereof.
Background
Boron Nitride (BN) is known as "white graphite", which has a structure similar to 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, chemical stability (excellent corrosion resistance), and the like. In recent years, with the vigorous development of materials, the materials are developed from zero-dimensional, one-dimensional, two-dimensional and the like to multi-dimensional structures. The boron nitride material is selected from the group consisting of nanotubes, nanoribbons, nanosheets, microplates, and the like, according to the dimensions, morphology, and dimensions. The controllable preparation of boron nitride micro-and nano-materials with different dimensions, shapes and sizes is a hot spot of current discipline research, and with the deep research of boron nitride materials, the boron nitride micro-and nano-materials have wide application in the aspects of strengthening and toughening of ceramic materials, adsorption of heavy metal ions and organic dyes, improvement of heat conducting performance of polymers and the like.
At present, boron nitride with different structures is prepared by a plurality of methods, such as a ball milling method, a high-pressure benzene heating method, a vapor deposition method and the like, and ammonia pentaborate, ammonia borane complex and magnesium oxide are used as raw materials, and after uniform ball milling, ammonia is introduced for protection for 6 hours, a BN nano tube-nano sheet hierarchical structure is obtained, wherein the length of the hierarchical structure is greater than 5 mu m, the middle of the hierarchical structure is a bamboo-shaped hollow structure, the inner tube 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 nano tube-nano sheet hierarchical structure has certain application potential in the field of ultraviolet light materials. However, the method is low in yield and unsuitable for mass production. Liu Bingsai and the like use boric acid and magnesium chloride as reaction raw materials, use sodium chloride or potassium chloride as cosolvent, mix by a certain proportion, anneal at 800-1000 ℃ to form boron-containing precursor, then introduce ammonia gas to protect at about 1100 ℃ for annealing, collect a one-dimensional hierarchical thin-wall BN micron tube, the internal tube diameter range is 0.4-2 um, the tube length is 5-60 um, the tube wall thickness is 30-100 nm, the tube surface is loaded with boron nitride nano-sheets, the sheets are mutually interwoven to form boron nitride sheets, the thickness of the boron nitride sheets is 40-80 nm, the boron nitride hierarchical structure obtained by the preparation method has important wide application prospect in ceramic reinforcement and toughening, the heat conducting property of the polymer is improved, but the nano-sheets of the structure are smaller, the morphology is irregular, the BN sheets are randomly interwoven on one piece without orientation, the surface area is small, and the adsorption property is weak.
Disclosure of Invention
The invention aims to solve the technical problem of providing a boron nitride hollow tube with a lamellar directional coverage formed tube wall and a preparation method thereof aiming at the defects in the prior art. The boron-containing precursor is obtained by utilizing the hydrothermal reaction of ammonia water, boric acid and magnesium nitrate as raw materials, and the boron nitride hollow tube with the lamellar directional coverage forming the tube wall is prepared by a two-step synthesis process of high-temperature nitridation combined with high-pressure reaction.
The invention adopts the technical proposal for solving the problems that:
a preparation method of a boron nitride hollow tube with a lamellar directional coverage formed tube wall mainly comprises the following steps:
(1) Boric acid and magnesium nitrate are mixed in water, and then ammonia water is added to adjust the pH value to 10 to 10.5, so as 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 nitriding product with ammonium chloride, and placing the mixture into a high-pressure reaction kettle for reaction to obtain the hollow boron nitride with the pipe 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 to 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, 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 atmosphere containing nitrogen is NH 3 The flow rate of the atmosphere and the nitrogen-containing atmosphere is 100 ml/min-200 ml/min, and the optimal flow rate of the atmosphere is 100ml/min.
According to the scheme, in the step (2), the calcination temperature is 850-1000 ℃ and the calcination heat preservation time is 30-60 min.
According to the scheme, in the step (3), the mass ratio of the nitriding product to the ammonium chloride is 1:1 to 2.
According to the scheme, in the step (3), the reaction time in the high-pressure reaction kettle is 1-2 h, and the reaction temperature is 500-600 ℃.
The boron nitride hollow tube material with the lamellar (scale-shaped) structure is obtained by the preparation method, the lamellar layers are regularly arranged in an oriented manner along the tube diameter direction to form the tube wall with the scale-shaped structure, the lamellar layer thickness is 10-20 nm, the number of lamellar layers is 1-3, the inner diameter range of the hollow tube is 0.2-1.2 mu m, the tube length is 0.6-2 mu m, and the tube wall thickness is 10-100 nm.
The invention can generate the following chemical reactions in the boron nitride hollow tube in the synthesis process:
Mg(NO 3 ) 2 (l)+H 3 BO 3 (l)+NH 3 . H 2 O(l)→MgBO 2 (OH)(s)+NH 4 NO 3 (l)+H 2 O(l) (1)
MgBO 2 (OH)(s)+NH 3 (g)→[B-Mg-O-N-H](s) (2)
[B-Mg-O-N-H](s)+NH 4 Cl(s)→BNMTs-BNnanoplates(BNMT-BNNPs)(s)+MgCl 2 (l)+H 2 (g)+H 2 O(l) (3)
the possible reaction mechanisms of the above synthesis process are: the boron source is from MgBO in solid state 2 (OH) precursor, mgBO with gradual rise of temperature during nitriding 2 The (OH) precursor gradually becomes liquid, part of boron element is separated out from the surface of the precursor to form gaseous boron oxide, and the boron element inside continuously diffuses outwards due to concentration difference to form MgBO 2 The (OH) precursor is taken as a template to react with external nitrogen active gas to form a boron nitride micron tube shell, and the boron-containing precursor coated with the BN shell is decomposed with ammonium chloride at high temperature and high pressure in a high-pressure reaction kettle to form active N.times.NH 3 And H 2 The mixed gases react to form a BN inner layer. Meanwhile, the active gaseous substances react with the B precursor, and simultaneously can erode the surface layer of the pipe under the special condition of closed self-generated 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 still keep regular arrangement along the pipe diameter axial direction, so that a few-layer fish scale-shaped 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 boron-containing precursor is prepared from the raw materials of simply and easily available boric acid, ammonia water and magnesium nitrate, the preliminary nitridation reaction is carried out in a tube furnace by taking the precursor as a boron source, and then the preliminary nitridation reaction is carried out with ammonium chloride to prepare the boron nitride hollow tube with the lamellar directional coverage forming the tube wall, so that the purity of the product reaches 99%, and the mass industrialized preparation is facilitated.
2. The small-layer fish scale-shaped hollow boron nitride structure with regular axial arrangement prepared by the invention is formed by self-assembly of nano sheets, which is not reported in the literature, and the special morphology greatly improves the specific surface area of the product and can reach 272.6m 2 g -1 Is obviously higher than the specific surface area (-25 m) of boron nitride powder on the market 2 g -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 plot of the BN sample obtained in example 1.
Detailed Description
For a better understanding of the present invention, the following examples are further illustrated, but are not limited to the following examples.
In the following examples, the morphology of the resulting product was observed with a FEI Quanta FEG 250 scanning electron microscope (FSEM); researching the internal microstructure of a sample by using a JEM2100-F type Transmission Electron Microscope (TEM), ultrasonically dispersing a product in absolute ethyl alcohol, and dripping the product onto a carbon film; x-ray diffraction analysis (XRD) using Rigaku D/MAX-LLIA type X-ray powder diffractometer
Figure BDA0003506883500000041
2 theta is 10-80 degrees; infrared spectroscopy (FTIR) testing using a Thermo Nexus470 fourier transform infrared spectrometer (thermonikov company, usa); specific surface area (BET) test Using TriStarII3200 type analyzer.
Comparative example 1
(1) Magnetic stirring at room temperature, H 3 BO 3 And Mg (NO) 3 ) 2 Mixing and dissolving in deionized water to make the concentration of the solution be 3mol/L and 2mol/L respectively, and then dropwise adding ammonia water with the concentration of 25% until the pH value is 10 to obtain a precursor solution. Then, 80ml of precursor solution is taken and put into a hydrothermal reaction kettle with a polytetrafluoroethylene lining and a capacity of 100ml, the temperature is heated to 200 ℃, the temperature is kept for 20 hours under isothermal conditions, then the mixture is naturally cooled to room temperature, the product is filtered, washed three times with deionized water, and vacuum-dried for 12 hours at 110 ℃ to obtain a boron-containing precursor;
(2) Placing the prepared boron-containing precursor into a tube furnace, vacuumizing, introducing ammonia gas with the flow rate of 150ml/min, preserving heat 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) Adding 30ml of 12mol/L hydrochloric acid into 20ml of distilled water, heating and stirring for 5 hours at 50 ℃, washing and centrifuging with deionized water for three times, washing with ethanol for two times, and finally drying in vacuum for 10 hours at 50 ℃ to obtain a low-crystallinity boron nitride tube with the surface not covered by the boron nitride nano-sheet, which is marked as a BN sample.
As shown in fig. 1, SEM spectra of BN samples prepared in this comparative example. As can be seen from the photo, the BN sample is a low-crystallinity boron nitride tubular object with the surface not covered by the boron nitride nano-sheet, the internal pipe diameter range is 0.1-0.3 mu m, the pipe length is 0.3-1 mu m, the pipe wall thickness is 10-100 nm, and the surface not covered by the boron nitride nano-sheet.
Example 1
The preparation method of the boron nitride hollow tube with the lamellar directional coverage forming the tube wall comprises the following steps:
(1) Magnetic stirring at room temperature, H 3 BO 3 And Mg (NO) 3 ) 2 Mixing and dissolving in deionized water to make the concentration of the solution be 3mol/L and 2mol/L respectively, and then dropwise adding ammonia water with the concentration of 25% until the pH value is 10 to obtain a precursor solution. Thereafter, 80ml of precursor was takenPlacing the body solution into a polytetrafluoroethylene-lined hydrothermal reaction kettle with the capacity of 100ml, heating to 200 ℃, keeping for 20 hours under isothermal conditions, naturally cooling to room temperature, filtering the product, washing with deionized water for three times, and vacuum drying at 110 ℃ for 12 hours to obtain a boron-containing precursor;
(2) Placing the prepared boron-containing precursor into a tube furnace, vacuumizing, introducing ammonia gas with the flow rate of 100ml/min, preserving heat 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) The nitriding product and ammonium chloride are mixed according to the mass ratio of 1:1, mixing and placing the mixture into a high-pressure reaction kettle to react for 1h 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 5 hours at 50 ℃, washing and centrifuging with deionized water for three times, washing with ethanol for two times, and finally drying in vacuum for 10 hours at 50 ℃ to obtain a boron nitride hollow tube with a lamellar (fish scale-shaped) structure on the tube wall, which is marked as a BN sample.
As shown in fig. 2, SEM spectra of BN samples prepared in this example. As shown in the photo, the BN sample is of 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 lamellar layers are regularly arranged along the tube diameter direction to form the tube wall with a fish scale-like structure, the lamellar layer thickness is 10-20 nm, and the number of boron nitride layers is 1-3.
As shown in fig. 3, HRTEM photographs of BN samples prepared in this example were obtained. From the photograph, clear lattice fringes can be observed, and the lattice spacing is about 0.34nm, which is consistent with the lattice constant of the (002) crystal face of h-BN, which is illustrated as h-BN material.
As shown in fig. 4, the XRD spectrum of the BN sample prepared in this example has 5 distinct diffraction main peaks, which are located at 2θ=26.76 °, 41.60 °, 50.14 °, 55.16 °, 75.93 °, respectively, and the peaks correspond to (002), (100), (102), (004) and (110) crystal planes (JCPDF No. 34-0421) of the h-BN crystal, respectively, so that the sample has no impurity phase and a purity higher than 99%.
As shown in FIG. 5, the present embodiment isThe FTIR spectrum of the obtained BN sample shows that 3 obvious characteristic absorption peaks are respectively positioned at 811, 1373 and 3411cm -1 Where it is located. Wherein 1373 and 811cm -1 The absorption peaks at the positions 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 -1 The absorption peak at this point is usually due to the adsorption of water or stretching vibration of O-H bonds in the surface mild oxidation.
As shown in FIG. 6, the nitrogen adsorption/desorption isotherm of the BN sample prepared in this example is that the sample belongs to the type IV adsorption/desorption isotherm with H3 hysteresis loop, N being near 1.0 when the relative pressure is close to 1.0 2 The adsorption capacity of the sample is obviously increased, the pore diameter of the sample contains macropores, and the specific surface area of the sample is 272.6m 2 g -1 。
Example 2
The preparation method of the boron nitride hollow tube with the lamellar directional coverage forming the tube wall comprises the following steps:
(1) Magnetic stirring at room temperature, H 3 BO 3 And Mg (NO) 3 ) 2 Mixing and dissolving in deionized water to make the concentration of the solution be 3mol/L and 2mol/L respectively, and then dropwise adding ammonia water with the concentration of 25% until the pH value is 10 to obtain a precursor solution. Then, 80ml of precursor solution is taken and put into a hydrothermal reaction kettle with a polytetrafluoroethylene lining and a capacity of 100ml, the temperature is heated to 200 ℃, the temperature is kept for 20 hours under isothermal conditions, then the mixture is naturally cooled to room temperature, the product is filtered, washed three times with deionized water, and vacuum-dried for 12 hours at 110 ℃ to obtain a boron-containing precursor;
(2) Placing the prepared boron-containing precursor into a tube furnace, vacuumizing, introducing ammonia gas with the flow rate of 150ml/min, preserving heat 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) The nitriding product and ammonium chloride are mixed according to the mass ratio of 1:1, mixing and placing the mixture into a high-pressure reaction kettle to react for 1h 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 5 hours at 50 ℃, washing and centrifuging with deionized water for three times, washing with ethanol for two times, and finally drying in vacuum for 10 hours at 50 ℃ to obtain a boron nitride hollow tube with a lamellar (fish scale-shaped) structure on the tube wall, which is marked as a BN sample.
Example 3
The preparation method of the boron nitride hollow tube with the lamellar directional coverage forming the tube wall comprises the following steps:
(1) Magnetic stirring at room temperature, H 3 BO 3 And Mg (NO) 3 ) 2 Mixing and dissolving in deionized water to make the concentration of the solution be 3mol/L and 2mol/L respectively, and then dropwise adding ammonia water with the concentration of 25% until the pH value is 10 to obtain a precursor solution. Then, 80ml of precursor solution is taken and put into a hydrothermal reaction kettle with a polytetrafluoroethylene lining and a capacity of 100ml, the temperature is heated to 200 ℃, the temperature is kept for 20 hours under isothermal conditions, then the mixture is naturally cooled to room temperature, the product is filtered, washed three times with deionized water, and vacuum-dried for 12 hours at 110 ℃ to obtain a boron-containing precursor;
(2) Placing the prepared boron-containing precursor into a tube furnace, vacuumizing, introducing ammonia gas with the flow rate of 200ml/min, preserving heat 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) The nitriding product and ammonium chloride are mixed according to the mass ratio of 1:1, mixing and placing the mixture into a high-pressure reaction kettle to react for 1h 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 5 hours at 50 ℃, washing and centrifuging with deionized water for three times, washing with ethanol for two times, and finally drying in vacuum for 10 hours at 50 ℃ to obtain a boron nitride hollow tube with a lamellar (fish scale-shaped) structure on the tube wall, which is marked as a BN sample.
Example 4
The preparation method of the boron nitride hollow tube with the lamellar directional coverage forming the tube wall comprises the following steps:
(1) Magnetic stirring at room temperature, H 3 BO 3 And Mg (NO) 3 ) 2 Mixing and dissolving in deionized water to make the concentration be 3mol/L and 2mol/L respectively, then dripping 25%To a pH of 10 to obtain a precursor solution. Then, 80ml of precursor solution is taken and put into a hydrothermal reaction kettle with a polytetrafluoroethylene lining and a capacity of 100ml, the temperature is heated to 200 ℃, the temperature is kept for 20 hours under isothermal conditions, then the mixture is naturally cooled to room temperature, the product is filtered, washed three times with deionized water, and vacuum-dried for 12 hours at 110 ℃ to obtain a boron-containing precursor;
(2) Placing the prepared boron-containing precursor into a tube furnace, vacuumizing, introducing ammonia gas with the flow rate of 100ml/min, preserving heat for 1h at 850 ℃, cooling to 200 ℃ along with the furnace, closing a vent valve, and naturally cooling to room temperature to obtain a nitriding product;
(3) The nitriding product and ammonium chloride are mixed according to the mass ratio of 1:1, mixing and placing the mixture into a high-pressure reaction kettle to react for 1h 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 5 hours at 50 ℃, washing and centrifuging with deionized water for three times, washing with ethanol for two times, and finally drying in vacuum for 10 hours at 50 ℃ to obtain a boron nitride hollow tube with a lamellar (fish scale-shaped) structure on the tube wall, which is marked as a BN sample.
Example 5
The preparation method of the boron nitride hollow tube with the lamellar directional coverage forming the tube wall comprises the following steps:
(1) Magnetic stirring at room temperature, H 3 BO 3 And Mg (NO) 3 ) 2 Mixing and dissolving in deionized water to make the concentration of the solution be 3mol/L and 2mol/L respectively, and then dropwise adding ammonia water with the concentration of 25% until the pH value is 10 to obtain a precursor solution. Then, 80ml of precursor solution is taken and put into a hydrothermal reaction kettle with a polytetrafluoroethylene lining and a capacity of 100ml, the temperature is heated to 200 ℃, the temperature is kept for 20 hours under isothermal conditions, then the mixture is naturally cooled to room temperature, the product is filtered, washed three times with deionized water, and vacuum-dried for 12 hours at 110 ℃ to obtain a boron-containing precursor;
(2) Placing the prepared boron-containing precursor into a tube furnace, vacuumizing, introducing ammonia gas with the flow rate of 100ml/min, preserving heat for 1h at 900 ℃, cooling to 200 ℃ along with the furnace, closing a vent valve, and naturally cooling to room temperature to obtain a nitriding product;
(3) The nitriding product and ammonium chloride are mixed according to the mass ratio of 1:1, mixing and placing the mixture into a high-pressure reaction kettle to react for 1h 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 5 hours at 50 ℃, washing and centrifuging with deionized water for three times, washing with ethanol for two times, and finally drying in vacuum for 10 hours at 50 ℃ to obtain a boron nitride hollow tube with a lamellar (fish scale-shaped) structure on the tube wall, which is marked as a BN sample.
The foregoing is merely a preferred embodiment of the present invention, and it should be noted that modifications and changes can be made by those skilled in the art without departing from the inventive concept and remain within the scope of the invention.

Claims (8)

1. The boron nitride hollow tube is characterized in that the lamellar layers are arranged into a tube wall in an oriented manner along the tube diameter direction, the number of the lamellar layers is 1-3, the lamellar layer thickness is 10-20 nm, the inner diameter range of the hollow tube is 0.2-1.2 mu m, the tube length is 0.6-2 mu m, and the tube wall thickness is 10-100 nm.
2. The method for preparing the boron nitride hollow tube with the lamellar directional coverage forming the tube wall as claimed in claim 1, which is characterized by comprising the following main steps:
(1) Mixing boric acid and magnesium nitrate, dissolving the mixture in water, and then adding ammonia water to adjust the pH 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 nitriding product with ammonium chloride, and placing the mixture into a high-pressure reaction kettle for reaction at the temperature of 500-600 ℃ for 1-2 hours to obtain the hollow boron nitride with the pipe wall having a lamellar structure.
3. The method for preparing a boron nitride hollow tube with a lamellar directional coverage forming a tube wall according to claim 2, wherein in the step (1), the molar ratio of boric acid to magnesium nitrate is 3: 2-1.
4. The method for preparing a boron nitride hollow tube with directional lamellar coverage forming a tube wall, according to claim 2, wherein in the step (1), boric acid and magnesium nitrate are mixed and dissolved in water, 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 a boron nitride hollow tube with a directional lamellar coverage forming 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 producing a boron nitride hollow tube having a tube wall formed by lamellar directional coverage as claimed in claim 2, wherein in the step (2), the atmosphere containing nitrogen is NH 3 The flow rate of the atmosphere is 100 ml/min-200 ml/min.
7. The method for preparing a boron nitride hollow tube with directional coverage of sheet layers to form a tube wall 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 a boron nitride hollow tube with lamellar directional coverage forming a tube wall according to claim 2, wherein in the step (3), the mass ratio of nitriding product to ammonium chloride is 1: and 1-2, mixing.
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