CN114751387A - Method for efficiently preparing boron nitride nanosheet - Google Patents
Method for efficiently preparing boron nitride nanosheet Download PDFInfo
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- CN114751387A CN114751387A CN202210374129.3A CN202210374129A CN114751387A CN 114751387 A CN114751387 A CN 114751387A CN 202210374129 A CN202210374129 A CN 202210374129A CN 114751387 A CN114751387 A CN 114751387A
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- 239000002135 nanosheet Substances 0.000 title claims abstract description 92
- 229910052582 BN Inorganic materials 0.000 title claims abstract description 64
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 title claims abstract description 64
- 238000000034 method Methods 0.000 title claims abstract description 12
- BIKXLKXABVUSMH-UHFFFAOYSA-N trizinc;diborate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]B([O-])[O-].[O-]B([O-])[O-] BIKXLKXABVUSMH-UHFFFAOYSA-N 0.000 claims abstract description 32
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 27
- 238000002360 preparation method Methods 0.000 claims abstract description 20
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims abstract description 17
- 229910052796 boron Inorganic materials 0.000 claims abstract description 14
- 238000004519 manufacturing process Methods 0.000 claims abstract description 7
- 239000000758 substrate Substances 0.000 claims abstract description 5
- 238000006243 chemical reaction Methods 0.000 claims description 41
- 238000004140 cleaning Methods 0.000 claims description 30
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 30
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical group Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 22
- 238000010438 heat treatment Methods 0.000 claims description 19
- 238000001035 drying Methods 0.000 claims description 17
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 claims description 14
- 239000002253 acid Substances 0.000 claims description 13
- 239000008367 deionised water Substances 0.000 claims description 10
- 229910021641 deionized water Inorganic materials 0.000 claims description 10
- 239000000047 product Substances 0.000 claims description 10
- 229910021538 borax Inorganic materials 0.000 claims description 7
- 235000010339 sodium tetraborate Nutrition 0.000 claims description 7
- BSVBQGMMJUBVOD-UHFFFAOYSA-N trisodium borate Chemical compound [Na+].[Na+].[Na+].[O-]B([O-])[O-] BSVBQGMMJUBVOD-UHFFFAOYSA-N 0.000 claims description 7
- 238000004321 preservation Methods 0.000 claims description 6
- 238000004506 ultrasonic cleaning Methods 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 5
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 4
- 229910021529 ammonia Inorganic materials 0.000 claims description 4
- 230000000694 effects Effects 0.000 claims description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 2
- 239000007795 chemical reaction product Substances 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 229910017604 nitric acid Inorganic materials 0.000 claims description 2
- 239000004552 water soluble powder Substances 0.000 claims description 2
- 239000011852 carbon nanoparticle Substances 0.000 claims 1
- 239000002055 nanoplate Substances 0.000 claims 1
- 239000002243 precursor Substances 0.000 abstract description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 abstract description 4
- 239000007769 metal material Substances 0.000 abstract description 2
- 229910052757 nitrogen Inorganic materials 0.000 abstract description 2
- 238000001556 precipitation Methods 0.000 abstract 1
- 230000002194 synthesizing effect Effects 0.000 abstract 1
- XIOUDVJTOYVRTB-UHFFFAOYSA-N 1-(1-adamantyl)-3-aminothiourea Chemical compound C1C(C2)CC3CC2CC1(NC(=S)NN)C3 XIOUDVJTOYVRTB-UHFFFAOYSA-N 0.000 description 16
- CDMADVZSLOHIFP-UHFFFAOYSA-N disodium;3,7-dioxido-2,4,6,8,9-pentaoxa-1,3,5,7-tetraborabicyclo[3.3.1]nonane;decahydrate Chemical compound O.O.O.O.O.O.O.O.O.O.[Na+].[Na+].O1B([O-])OB2OB([O-])OB1O2 CDMADVZSLOHIFP-UHFFFAOYSA-N 0.000 description 16
- 239000000203 mixture Substances 0.000 description 8
- 238000003756 stirring Methods 0.000 description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 6
- 229910021389 graphene Inorganic materials 0.000 description 5
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 4
- 230000001276 controlling effect Effects 0.000 description 4
- 230000001105 regulatory effect Effects 0.000 description 4
- 239000000725 suspension Substances 0.000 description 4
- 238000005303 weighing Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 3
- 239000011812 mixed powder Substances 0.000 description 3
- 238000005121 nitriding Methods 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- 238000000151 deposition Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 239000011787 zinc oxide Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000010292 electrical insulation Methods 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000005554 pickling Methods 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- 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
-
- 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
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—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
- C01P2004/20—Particle morphology extending in two dimensions, e.g. plate-like
Abstract
The invention relates to a preparation method of a boron nitride nanosheet, and belongs to the technical field of inorganic non-metallic materials. Firstly, synthesizing nano flaky zinc borate as a boron source precursor and a substrate template, and ammonia gas as a nitrogen source, so that a boron nitride nanosheet which is good in appearance and has a micron-sized transverse dimension is prepared at a lower temperature; meanwhile, the nanosheet-shaped zinc borate precursor is prepared by a one-step precipitation method, so that the yield is high, the operation is simple, the method for preparing the boron nitride nanosheet has the advantages of adjustable size, high yield and capability of mass production, and a foundation is provided for the mass application of the boron nitride nanosheet.
Description
Technical Field
The invention belongs to the technical field of inorganic non-metallic materials, and particularly relates to a preparation method of a boron nitride nanosheet.
Background
This background section disclosure is not necessarily to be construed as prior art.
In 2004, Geim and Novoselov produced graphene (graphene) materials that existed stably, and demonstrated that graphene has unique and excellent properties, thereby raising the hot tide of research on graphene materials. With the continuous and intensive research, other two-dimensional layered materials with similar structures are continuously increased, and the boron nitride nanosheet has the unique electrical insulation and high temperature oxidation resistance on the basis of the similar excellent performance of graphene, so that the boron nitride nanosheet attracts wide attention.
At present, people have relatively deep knowledge on the relevant properties of the boron nitride nanosheets, and the boron nitride nanosheets are prepared by various methods, so that the application of the boron nitride nanosheets is further researched. However, the existing preparation method is mainly used for obtaining the boron nitride nanosheet by peeling the hexagonal boron nitride from top to bottom. However, the bonding force between hexagonal boron nitride layers is relatively strong to graphite, and the hexagonal boron nitride layers are difficult to strip, so that the yield is low. If very strong mechanical force is used for stripping hexagonal boron nitride, although the yield is improved, the mass of the prepared boron nitride nanosheet is inevitably reduced, more crystal defects exist, and the later application of the boron nitride nanosheet is limited. The boron nitride nanosheets prepared by other preparation methods, such as the existing 'bottom-up' chemical vapor deposition method, also have the problems of low yield and high price, which also limits the further application of the boron nitride nanosheets in many fields. Therefore, the development of a more efficient and stable process for preparing the boron nitride nanosheet remains the focus and difficulty of research in the field.
Disclosure of Invention
Based on the technical background, the invention aims to provide an efficient preparation method of boron nitride nanosheets. In order to realize the technical purpose, the invention takes the zinc borate nanosheet as a boron source, simultaneously takes the zinc borate nanosheet as a substrate template for reaction, takes ammonia gas as a nitrogen source, and prepares the boron nitride nanosheet through high-temperature nitridation reaction. And continuously diffusing boron elements in the zinc borate nanosheets at the temperature close to the melting point temperature to the surface in the reaction process, reacting with ammonia gas, depositing a layer of boron nitride nanosheets on the surface of the zinc borate nanosheets, leaving zinc oxide on the inner layer, and then washing away the zinc oxide through concentrated hydrochloric acid ultrasonic pickling to obtain pure boron nitride nanosheets. The preparation method has the advantages of stability, reliability, simple operation, lower equipment cost, easily obtained raw materials and high yield.
Based on the technical effects, the first aspect of the invention provides a preparation method of a boron nitride nanosheet, and the preparation method comprises the steps of taking a zinc borate nanosheet as a boron source, and carrying out high-temperature heating reaction in an ammonia atmosphere to obtain the boron nitride nanosheet.
In the preparation method, the zinc borate nanosheet serves as a modeling agent and a boron source at the same time, and a flaky template is provided for the deposition of boron nitride. The invention further provides a preparation method of the zinc borate nanosheet, which is prepared by heating zinc nitrate and sodium borate, and the preparation method comprises the following steps: respectively heating the water solutions of zinc nitrate and sodium borate to 65-75 ℃, mixing the two solutions, and heating in a water bath at 65-75 ℃ for 18-24 hours to obtain the zinc nitrate and sodium borate water-soluble powder.
Furthermore, the concentration of the zinc nitrate solution is 0.1-0.3 mol/L.
Further, the concentration of the sodium borate solution is 0.05-0.15 mol/L.
And after the water bath reaction is finished, cleaning and drying a reaction product to obtain the zinc borate nanosheet, wherein the drying temperature is 55-65 ℃, and the drying time is 8-12 h.
Preferably, the boron source and ammonia gas are heated at high temperature in the following specific manner: and (2) placing a boron source in a tubular furnace, introducing ammonia gas to carry out high-temperature reaction, wherein the reaction temperature is 800-1100 ℃, the heating rate is 8-12 ℃/min, and the heat preservation time is 2-4 h.
Further, the flow rate of the ammonia gas is 65-75 sccm; furthermore, the flow rate is 68 to 72sccm, and a specific example is 71.9 sccm.
Preferably, the method further comprises the steps of cleaning and drying the product after the high-temperature heating is finished; the cleaning is carried out by adopting acid liquor, and the acid liquor is hydrochloric acid, nitric acid or sulfuric acid solution.
Further, ultrasonic cleaning is carried out on the acid cleaning by adopting a hydrochloric acid solution, the concentration of the hydrochloric acid is 2-5 mol/L, and the time of the ultrasonic cleaning is 3-5 h.
And the ultrasonic cleaning step further comprises a water cleaning step, the water cleaning step adopts deionized water to carry out centrifugal cleaning, the cleaning frequency can be adjusted according to the cleaning effect, for example, 3-5 times, and the boron nitride nanosheet is obtained by drying at 55-65 ℃ for 8-12 hours after the cleaning is finished.
The thickness of the boron nitride nanosheet prepared by the method is 5-14nm, the transverse size can be regulated and controlled from nano-scale to micron-scale, and the boron nitride nanosheet has the advantage of mass production; in addition, the single-time yield of the preparation method can reach gram level, and the size of the zinc borate nanosheet can be controlled by controlling the reaction time of the precursor; in addition, the size and the thickness of the boron nitride nanosheet can be regulated and controlled in a mode of controlling parameters such as the temperature, the reaction time and the like of ammonia gas nitridation. The embodiment proves that the size of the zinc borate nanosheet is gradually increased along with the extension of the water bath reaction time, and the size of the boron nitride nanosheet can be controlled by controlling the transverse size of the zinc borate nanosheet because the zinc borate nanosheet is used as a substrate template; in addition, the quality and the thickness of the boron nitride nanosheet are closely related to parameters such as temperature, time and the like of ammonia gas nitriding reaction, so that the quality and the thickness of the prepared boron nitride nanosheet can be further regulated and controlled by regulating and controlling ammonia gas nitriding parameters.
The beneficial effects of one or more of the above technical schemes are:
1. the preparation method of the boron nitride nanosheet provided by the invention can realize mass preparation of the boron nitride nanosheet, obviously improves the yield of a single reaction compared with modes such as mechanical stripping and vapor deposition, and effectively meets the practical application of the boron nitride nanosheet.
2. The raw materials adopted in the preparation method are easy to obtain, the cost is low, the production equipment is relatively simple, the operation is convenient, and the industrial expanded production is easy to realize.
3. In addition, the invention takes the zinc borate nanosheet with thinner thickness as a boron source and a substrate template, thereby realizing the controllable preparation of the boron nitride nanosheet with the transverse dimension from nano-scale to micron-scale, and adjusting the transverse dimension of the boron nitride nanosheet according to the use purpose.
Drawings
The accompanying drawings, which are incorporated in and constitute a part of this specification, are included to provide a further understanding of the invention, and are included to illustrate an exemplary embodiment of the invention and not to limit the invention.
FIG. 1 is a scanning electron microscope photo of a flake zinc borate precursor nanosheet prepared in examples 1 to 3 by water-domain reaction for 24 hours and in example 4 by water-bath reaction for 18 hours, and it can be clearly seen that the size of the zinc borate nanosheet subjected to the reaction for 18 hours is much smaller than that of the zinc borate nanosheet subjected to the reaction for 24 hours;
wherein, the precursor nano-sheet is prepared by reacting for 24 hours in a figure 1A, and the magnification is 20000 times;
FIG. 1B shows that precursor nanosheets are prepared by reaction for 18 hours, and the magnification of the nanosheets is 20000 times;
FIG. 2 is a scanning electron micrograph of the boron nitride nanosheets prepared in examples 1 to 4 of the present invention, and it can be seen from FIGS. 2A, 2B, and 2C of examples 1 to 3 that the surface of the prepared boron nitride nanosheets tends to be smooth and the size thereof also increases as the ammonia nitriding temperature increases from 800 ℃ to 1000 ℃; the boron nitride nanosheet at 800 ℃ has low reaction temperature and slow diffusion of a boron source in the reaction process, so that the prepared boron nitride nanosheet has a plurality of clastic nanosheets and is poor in quality; the boron nitride nanosheets prepared at 900 ℃ and 1000 ℃ have good quality, smooth surfaces and micron-sized transverse dimensions; fig. 2D shows that the transverse size of the obtained boron nitride nanosheet is very small and the size is nanometer after the zinc borate nanosheet subjected to water bath reaction for 18 hours is used as a boron source and subjected to nitridation at 900 ℃.
Wherein, the magnification of fig. 2A, 2B, 2C is 10000 times;
fig. 2D magnifies 25000 times.
FIG. 3 is a scanning electron microscope magnified image of a single sheet of boron nitride nanosheet prepared in example 2 of the present invention;
wherein, the magnification is 30000 times.
FIG. 4 is an AFM spectrum of boron nitride nanosheets prepared in example 3 of the present invention.
FIG. 5 is an XRD spectrum of a boron nitride nanosheet prepared in embodiments 1-3 of the present invention.
Detailed Description
It is to be understood that the following detailed description is exemplary and is intended to provide further explanation of the invention as claimed. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs.
It is noted that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of exemplary embodiments according to the invention. As used herein, the singular forms "a", "an" and "the" are intended to include the plural forms as well, and it should be understood that when the terms "comprises" and/or "comprising" are used in this specification, they specify the presence of stated features, steps, operations, devices, components, and/or combinations thereof, unless the context clearly indicates otherwise.
In order to make the technical solutions of the present invention more clearly understood by those skilled in the art, the technical solutions of the present invention will be described in detail below with reference to specific embodiments.
Example 1:
(1) weighing 0.02mol of zinc nitrate hexahydrate and 0.01mol of sodium borate decahydrate, respectively adding the zinc nitrate hexahydrate and the sodium borate decahydrate into two beakers filled with 100mL of deionized water, stirring the mixture for 30 minutes in a constant-temperature stirring water bath, and heating the mixture to 70 ℃ until the zinc nitrate hexahydrate and the sodium borate decahydrate are completely dissolved;
(2) pouring the zinc nitrate hexahydrate solution into a stirred sodium borate decahydrate solution at a constant speed, and reacting for 24 hours at 70 ℃;
(3) centrifugally cleaning a product after the water bath reaction for 3 times, drying at 60 ℃ for more than 10h, and collecting to obtain zinc borate nanosheets;
(4) carrying out high-temperature reaction on the obtained zinc borate nanosheet and ammonia gas in a tubular furnace, wherein the heating rate is 10 ℃/min, the reaction temperature is 800 ℃, the heat preservation time is 3h, and the flow of the ammonia gas is 71.9sccm in the reaction process; (5) adding the product after the high-temperature reaction into a hydrochloric acid solution with the concentration of 2mol/L for ultrasonic acid cleaning for 4 hours;
(6) and centrifugally cleaning the suspension subjected to ultrasonic acid cleaning by using deionized water for 3 times, drying at 60 ℃ for more than 10 hours, and collecting to obtain the boron nitride nanosheet.
Example 2:
(1) weighing 0.02mol of zinc nitrate hexahydrate and 0.01mol of sodium borate decahydrate, respectively adding the zinc nitrate hexahydrate and the sodium borate decahydrate into two beakers filled with 100mL of deionized water, stirring the mixture for 30 minutes in a constant-temperature stirring water bath, and heating the mixture to 70 ℃ until the zinc nitrate hexahydrate and the sodium borate decahydrate are completely dissolved;
(2) pouring the zinc nitrate hexahydrate solution into a stirred sodium borate decahydrate solution at a constant speed, and reacting for 24 hours at 70 ℃;
(3) centrifugally cleaning a product after the water bath reaction for 3 times, drying at 60 ℃ for more than 10h, and collecting to obtain zinc borate nanosheets;
(4) carrying out high-temperature reaction on the mixed powder obtained from the obtained zinc borate nanosheets and ammonia gas in a tubular furnace, wherein the heating rate is 10 ℃/min, the reaction temperature is 900 ℃, the heat preservation time is 3h, and the flow of the ammonia gas is 71.9sccm in the reaction process;
(5) adding the product after the high-temperature reaction into a hydrochloric acid solution with the concentration of 2mol/L for ultrasonic acid cleaning for 4 hours;
(6) and centrifugally cleaning the suspension subjected to ultrasonic acid cleaning by using deionized water for 3 times, drying at 60 ℃ for more than 10 hours, and collecting to obtain the boron nitride nanosheet.
Example 3:
(1) weighing 0.02mol of zinc nitrate hexahydrate and 0.01mol of sodium borate decahydrate, respectively adding the zinc nitrate hexahydrate and the sodium borate decahydrate into two beakers filled with 100mL of deionized water, stirring the mixture in a constant-temperature stirring water bath for 30 minutes, and heating the mixture to 70 ℃ until the zinc nitrate hexahydrate and the sodium borate decahydrate are completely dissolved;
(2) Pouring the zinc nitrate hexahydrate solution into a stirred sodium borate decahydrate solution at a constant speed, and reacting for 24 hours at 70 ℃;
(3) centrifugally cleaning a product after the water bath reaction for 3 times, drying at 60 ℃ for more than 10h, and collecting to obtain zinc borate nanosheets;
(4) carrying out high-temperature reaction on the mixed powder obtained from the obtained zinc borate nanosheets and ammonia gas in a tubular furnace, wherein the heating rate is 10 ℃/min, the reaction temperature is 1000 ℃, the heat preservation time is 3h, and the flow of the ammonia gas in the reaction process is 71.9 sccm;
(5) adding the product after the high-temperature reaction into a hydrochloric acid solution with the concentration of 2mol/L for ultrasonic acid cleaning for 4 hours;
(6) centrifugally cleaning the ultrasonically-acid-washed suspension by using deionized water for 3 times, drying at 60 ℃ for more than 10 hours, and collecting to obtain the boron nitride nanosheet.
Example 4:
(1) weighing 0.02mol of zinc nitrate hexahydrate and 0.01mol of sodium borate decahydrate, respectively adding the zinc nitrate hexahydrate and the sodium borate decahydrate into two beakers filled with 100mL of deionized water, stirring the mixture in a constant-temperature stirring water bath for 30 minutes, and heating the mixture to 70 ℃ until the zinc nitrate hexahydrate and the sodium borate decahydrate are completely dissolved;
(2) pouring the zinc nitrate hexahydrate solution into a stirred sodium borate decahydrate solution at a constant speed, and reacting for 18 hours at 70 ℃;
(3) centrifugally cleaning the product after the water bath reaction for 3 times, drying at 60 ℃ for more than 10h, and collecting to obtain zinc borate nanosheets;
(4) Carrying out high-temperature reaction on the mixed powder obtained from the obtained zinc borate nanosheets and ammonia gas in a tubular furnace, wherein the heating rate is 10 ℃/min, the reaction temperature is 900 ℃, the heat preservation time is 3h, and the flow of the ammonia gas is 71.9sccm in the reaction process;
(5) adding the product after the high-temperature reaction into a hydrochloric acid solution with the concentration of 2mol/L for ultrasonic acid cleaning for 4 hours;
(6) and centrifugally cleaning the suspension subjected to ultrasonic acid cleaning by using deionized water for 3 times, drying at 60 ℃ for more than 10 hours, and collecting to obtain the boron nitride nanosheet.
The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. The preparation method of the boron nitride nanosheet is characterized in that the boron nitride nanosheet is obtained by heating at high temperature in an ammonia atmosphere by taking a zinc borate nanosheet as a boron source.
2. A method of producing boron nitride nanoplates as described in claim 1, wherein the zinc borate nanoplates are produced in the following manner: respectively heating the water solutions of zinc nitrate and sodium borate to 65-75 ℃, mixing the two solutions, and heating in a water bath at 65-75 ℃ for 18-24 hours to obtain the zinc nitrate and sodium borate water-soluble powder.
3. A method of preparing boron nitride nanosheets as defined in claim 2, wherein the zinc nitrate solution has a concentration of 0.1 to 0.3 mol/L;
or the concentration of the sodium borate solution is 0.05-0.15 mol/L.
4. The preparation method of the boron nitride nanosheet of claim 2, wherein after the water bath reaction is finished, the reaction product is washed and dried to obtain the zinc borate nanosheet, wherein the drying temperature is 55-65 ℃, and the drying time is 8-12 h.
5. A method for preparing boron nitride nanosheets according to claim 1, wherein the boron source is zinc borate nanosheets prepared under different reaction conditions, and the zinc borate nanosheets are simultaneously used as a substrate template for preparing boron nitride nanosheets.
6. A method of making boron nitride nanoplates as described in claim 1, wherein the boron source and ammonia are heated at high temperature in the following manner: and (2) placing a boron source in a tubular furnace, introducing ammonia gas to carry out high-temperature reaction, wherein the reaction temperature is 800-1100 ℃, the heating rate is 8-12 ℃/min, and the heat preservation time is 2-4 h.
7. A method for producing boron nitride nanosheets according to claim 6, wherein the flow rate of the ammonia gas is 70 to 140 sccm; further, the amount of the carbon nano-particles is 70 to 72sccm, specifically 71.9 sccm.
8. A method of preparing boron nitride nanoplates as defined in claim 6, further comprising the steps of washing and drying the product after the high temperature heating is completed; the cleaning is carried out by adopting acid liquor, and the acid liquor is hydrochloric acid, nitric acid or sulfuric acid solution.
9. The preparation method of boron nitride nanosheets according to claim 8, wherein the acid washing is carried out by ultrasonic cleaning with a hydrochloric acid solution, the hydrochloric acid concentration is 1.5-2.5 mol/L, and the ultrasonic cleaning time is 3-5 h.
10. The preparation method of boron nitride nanosheets as claimed in claim 9, further comprising a water washing step after the ultrasonic cleaning, wherein the water washing step is performed by centrifugal cleaning with deionized water, the number of times of cleaning can be adjusted according to the cleaning effect, for example, 3 to 5 times, and the boron nitride nanosheets are obtained by drying at 60 to 80 ℃ for 8 to 12 hours after the cleaning is completed.
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| CN202210374129.3A CN114751387B (en) | 2022-04-11 | 2022-04-11 | Method for efficiently preparing boron nitride nanosheets |
| PCT/CN2022/142028 WO2023197682A1 (en) | 2022-04-11 | 2022-12-26 | Method for efficiently preparing boron nitride nanosheet |
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| CN202210374129.3A CN114751387B (en) | 2022-04-11 | 2022-04-11 | Method for efficiently preparing boron nitride nanosheets |
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| CN115448264A (en) * | 2022-08-31 | 2022-12-09 | 山东大学 | Preparation method of porous boron nitride nanosheet |
| WO2023197682A1 (en) * | 2022-04-11 | 2023-10-19 | 山东大学 | Method for efficiently preparing boron nitride nanosheet |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2009155176A (en) * | 2007-12-27 | 2009-07-16 | Teijin Ltd | Boron nitride nanofiber and method of manufacturing the same |
| CN106829888A (en) * | 2015-12-04 | 2017-06-13 | 中国科学院苏州纳米技术与纳米仿生研究所 | Boron nitride nanosheet powder and its magnanimity preparation method |
| CN107640750A (en) * | 2016-07-22 | 2018-01-30 | 中国科学院苏州纳米技术与纳米仿生研究所 | Boron nitride nanosheet powder and its inexpensive batch preparation |
| US20190127222A1 (en) * | 2016-07-22 | 2019-05-02 | Suzhou Institute Of Nano-Tech And Nano-Bionics (Sinano), Chinese Academy Of Sciences | Boron Nitride Nanomaterial, and Preparation Method and Use Thereof |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2009155176A (en) * | 2007-12-27 | 2009-07-16 | Teijin Ltd | Boron nitride nanofiber and method of manufacturing the same |
| CN106829888A (en) * | 2015-12-04 | 2017-06-13 | 中国科学院苏州纳米技术与纳米仿生研究所 | Boron nitride nanosheet powder and its magnanimity preparation method |
| CN107640750A (en) * | 2016-07-22 | 2018-01-30 | 中国科学院苏州纳米技术与纳米仿生研究所 | Boron nitride nanosheet powder and its inexpensive batch preparation |
| US20190127222A1 (en) * | 2016-07-22 | 2019-05-02 | Suzhou Institute Of Nano-Tech And Nano-Bionics (Sinano), Chinese Academy Of Sciences | Boron Nitride Nanomaterial, and Preparation Method and Use Thereof |
Non-Patent Citations (1)
| Title |
|---|
| 高平强等: ""一步沉淀法合成片状纳米硼酸锌及其性能表征"" * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2023197682A1 (en) * | 2022-04-11 | 2023-10-19 | 山东大学 | Method for efficiently preparing boron nitride nanosheet |
| CN115448264A (en) * | 2022-08-31 | 2022-12-09 | 山东大学 | Preparation method of porous boron nitride nanosheet |
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