CN114751387B - Method for efficiently preparing boron nitride nanosheets - Google Patents
Method for efficiently preparing boron nitride nanosheets Download PDFInfo
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- 239000002135 nanosheet Substances 0.000 title claims abstract description 84
- 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 15
- 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 31
- 238000002360 preparation method Methods 0.000 claims abstract description 18
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims abstract description 14
- 229910052796 boron Inorganic materials 0.000 claims abstract description 14
- 229910021529 ammonia Inorganic materials 0.000 claims abstract description 6
- 239000000758 substrate Substances 0.000 claims abstract description 3
- 238000006243 chemical reaction Methods 0.000 claims description 42
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 26
- 239000000243 solution Substances 0.000 claims description 23
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 22
- 238000004140 cleaning Methods 0.000 claims description 21
- 238000010438 heat treatment Methods 0.000 claims description 20
- 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 12
- 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
- 239000002253 acid Substances 0.000 claims description 8
- 238000005554 pickling Methods 0.000 claims description 7
- 229910021538 borax Inorganic materials 0.000 claims description 6
- 238000004321 preservation Methods 0.000 claims description 6
- 235000010339 sodium tetraborate Nutrition 0.000 claims description 6
- BSVBQGMMJUBVOD-UHFFFAOYSA-N trisodium borate Chemical compound [Na+].[Na+].[Na+].[O-]B([O-])[O-] BSVBQGMMJUBVOD-UHFFFAOYSA-N 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
- 239000007864 aqueous solution Substances 0.000 claims description 4
- 238000004506 ultrasonic cleaning Methods 0.000 claims description 4
- 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
- 239000002243 precursor Substances 0.000 abstract description 7
- 238000004519 manufacturing process Methods 0.000 abstract description 5
- 239000000463 material Substances 0.000 abstract description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 abstract description 4
- 229910052757 nitrogen Inorganic materials 0.000 abstract description 2
- 238000001556 precipitation Methods 0.000 abstract 1
- 230000002194 synthesizing effect Effects 0.000 abstract 1
- 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 12
- XIOUDVJTOYVRTB-UHFFFAOYSA-N 1-(1-adamantyl)-3-aminothiourea Chemical compound C1C(C2)CC3CC2CC1(NC(=S)NN)C3 XIOUDVJTOYVRTB-UHFFFAOYSA-N 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
- 239000002064 nanoplatelet Substances 0.000 description 6
- 229910021389 graphene Inorganic materials 0.000 description 5
- 238000005121 nitriding Methods 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
- 239000000725 suspension Substances 0.000 description 4
- 238000005303 weighing Methods 0.000 description 4
- JGPSMWXKRPZZRG-UHFFFAOYSA-N zinc;dinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O JGPSMWXKRPZZRG-UHFFFAOYSA-N 0.000 description 4
- 239000011812 mixed powder Substances 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- 230000001105 regulatory effect Effects 0.000 description 3
- 230000000694 effects Effects 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
- 239000011787 zinc oxide Substances 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 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
- 238000000151 deposition Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 238000009413 insulation Methods 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
- 238000001228 spectrum Methods 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B21/00—Nitrogen; Compounds thereof
- C01B21/06—Binary compounds of nitrogen with metals, with silicon, or with boron, or with carbon, i.e. nitrides; Compounds of nitrogen with more than one metal, silicon or boron
- C01B21/064—Binary compounds of nitrogen with metals, with silicon, or with boron, or with carbon, i.e. nitrides; Compounds of nitrogen with more than one metal, silicon or boron with boron
- C01B21/0646—Preparation by pyrolysis of boron and nitrogen containing compounds
-
- 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
-
- 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 nonmetallic materials. Firstly, synthesizing nano flaky zinc borate serving as a precursor boron source and a substrate template, and ammonia serving as a nitrogen source, so as to prepare the boron nitride nano tablet with good morphology and micron-sized transverse dimension at a lower temperature; meanwhile, as the nano flaky zinc borate precursor is prepared by adopting a one-step precipitation method, the yield is high, and the operation is simple, the method for preparing the boron nitride nano tablet has the advantages of adjustable size, high yield and mass production, and provides a foundation for mass application of the boron nitride nano tablet.
Description
Technical Field
The invention belongs to the technical field of inorganic nonmetallic 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 prepared graphene (graphene) materials which exist stably, and proved that graphene has unique and excellent properties, so that the scientific community has raised 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 nano-sheet has the unique electric insulation and high-temperature oxidation resistance properties on the basis of the similar excellent properties of graphene, so that the boron nitride nano-sheet is widely focused.
At present, the related properties of the boron nitride nano-sheet are well known, and various methods are adopted to prepare the boron nitride nano-sheet, so that further research on the application of the boron nitride nano-sheet is also carried out. However, since the existing preparation method mainly peels off hexagonal boron nitride from top to bottom to obtain boron nitride nano-sheets. However, the bonding force between the hexagonal boron nitride layers is relatively strong compared with that of graphite, so that the hexagonal boron nitride layers are difficult to peel off, and the yield is low. If the hexagonal boron nitride is stripped by using very strong mechanical force, although the yield is improved, the quality of the prepared boron nitride nano-sheet is inevitably reduced, more crystal defects exist, and the later application of the boron nitride nano-sheet is limited. Other preparation methods, such as the chemical vapor deposition method of 'bottom-up' at the present stage, also have the problems of low yield and higher price, which also limits the further application of the boron nitride nano-sheet in a plurality of fields. Therefore, developing a more efficient and stable process for preparing boron nitride nanoplatelets remains a major and difficult point of research in the art.
Disclosure of Invention
Based on the technical background, the invention aims to provide a high-efficiency preparation method of boron nitride nanosheets. In order to achieve the technical purpose, the invention prepares the boron nitride nano-sheet by taking the zinc borate nano-sheet as a boron source, taking the zinc borate nano-sheet as a reaction base template, taking ammonia gas as a nitrogen source and performing high-temperature nitridation reaction. And in the reaction process, boron element in the zinc borate nano sheet at the temperature near the melting point continuously diffuses to the surface to react with ammonia gas, a layer of boron nitride nano sheet is deposited on the surface of the zinc borate nano sheet, zinc oxide is left on the inner layer, and then the zinc oxide is washed off by concentrated hydrochloric acid ultrasonic pickling, so that the pure boron nitride nano sheet is obtained. The preparation method has the advantages of stability, reliability, simplicity in operation, lower equipment cost, readily available raw materials and capability of yielding.
Based on the technical effects, the first aspect of the invention provides a preparation method of boron nitride nano-sheets, which comprises the steps of taking zinc borate nano-sheets as a boron source, and carrying out high-temperature heating reaction in an ammonia atmosphere to obtain the boron nitride nano-sheets.
In the preparation method, the zinc borate nano-sheet simultaneously serves as a model agent and a boron source, and a sheet template is provided for the deposition of boron nitride. The invention further provides a preparation method of the zinc borate nano-sheet, which adopts zinc nitrate and sodium borate to heat and prepare, and comprises the following steps: heating the aqueous solution of zinc nitrate and sodium borate to 65-75 ℃ respectively, 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 aqueous solution.
Further, 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 the reaction product to obtain the zinc borate nano-sheet, wherein the drying temperature is 55-65 ℃ and the drying time is 8-12 h.
Preferably, the concrete mode of heating the boron source and the ammonia gas at high temperature is as follows: and (3) placing a boron source in a tube furnace, introducing ammonia gas for 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; further, 68 to 72sccm, and a specific example is 71.9sccm.
Preferably, the high-temperature heating is finished and then the method further comprises the steps of cleaning and drying the product; the cleaning is performed by adopting acid liquor, and the acid liquor is hydrochloric acid, nitric acid or sulfuric acid solution.
Further, the pickling is carried out by adopting hydrochloric acid solution for ultrasonic cleaning, the concentration of hydrochloric acid is 2-5 mol/L, and the time of ultrasonic cleaning is 3-5 h.
The ultrasonic cleaning step further comprises a water washing step, wherein deionized water is adopted for centrifugal cleaning, the cleaning times can be adjusted according to the cleaning effect, for example, 3-5 times, and the boron nitride nanosheets are obtained after the completion of cleaning and drying at 55-65 ℃ for 8-12 hours.
The thickness of the boron nitride nanosheets prepared in the mode is between 5 and 14nm, the transverse dimension can realize the regulation and control preparation from nano level to micron level, and the boron nitride nanosheets have the advantage of mass production; in addition, the single yield of the preparation method can reach gram level, and the size of the zinc borate nano-sheet can be controlled by controlling the reaction time of the precursor; in addition, the size and thickness of the boron nitride nanosheets can be regulated and controlled in a mode of controlling parameters such as the temperature, the reaction time and the like of ammonia nitriding. The embodiment proves that the size of the zinc borate nano sheet gradually increases along with the extension of the water bath reaction time, and the size of the boron nitride nano sheet can be controlled by controlling the transverse size of the zinc borate nano sheet because the zinc borate nano sheet is used as a base template; in addition, the quality and thickness of the boron nitride nano-sheet are also closely related to parameters such as the temperature, time and the like of the ammonia nitriding reaction, so that the quality and thickness of the prepared boron nitride nano-sheet can be further regulated and controlled by regulating and controlling the ammonia nitriding parameters.
The beneficial effects of the above technical scheme are:
1. the preparation method of the boron nitride nanosheets can realize mass preparation of the boron nitride nanosheets, remarkably improves the yield of single reaction compared with the modes of mechanical stripping, vapor deposition and the like, and effectively meets the practical application of the boron nitride nanosheets.
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 expansion production is easy to realize.
3. In addition, the invention takes the zinc borate nano-sheet with thinner thickness as the boron source and the substrate template, realizes the controllable preparation of the boron nitride nano-sheet with the nano-scale to micro-scale transverse dimension, and can adjust the transverse dimension of the boron nitride nano-sheet according to the use purpose.
Drawings
The accompanying drawings, which are included to provide a further understanding of the invention and are incorporated in and constitute a part of this specification, illustrate embodiments of the invention and together with the description serve to explain the invention.
FIG. 1 is a scanning electron microscope photograph of a flaky zinc borate precursor nano-sheet prepared by a water-domain reaction 24h in examples 1 to 3 and a water-bath reaction 18h in example 4, and it can be clearly seen that the size of the zinc borate nano-sheet in the reaction 18h is far smaller than that of the zinc borate nano-sheet in the reaction 24h;
wherein, FIG. 1A is a reaction for 24 hours to prepare a precursor nano-sheet, the magnification of which is 20000 times;
FIG. 1B shows that precursor nano-sheets are prepared by reaction for 18 hours, and the magnification of the precursor nano-sheets is 20000 times;
FIG. 2 is a scanning electron microscope photograph of boron nitride nanoplatelets 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 nanoplatelets tends to be smooth and the size thereof increases as the nitriding temperature of ammonia gas increases from 800 to 1000 ℃; the boron nitride nano-sheet at 800 ℃ has low reaction temperature, and the boron source diffuses slowly in the reaction process, so that the prepared boron nitride nano-sheet has a plurality of chipped nano-sheets and has poor quality; the boron nitride nano-sheet prepared at 900 ℃ and 1000 ℃ has good quality, smooth surface and transverse dimension in micron order; fig. 2D shows that after nitriding at 900 ℃ using zinc borate nano-sheets obtained by water bath reaction for 18h as a boron source, the obtained boron nitride nano-sheets have very small transverse dimension and nano-scale dimension.
Wherein, the magnification of fig. 2A, 2B, 2C is 10000 times;
fig. 2D is at 25000 magnification.
FIG. 3 is an enlarged image of a monolithic scanning electron microscope of the boron nitride nanoplatelets prepared in example 2 of the present invention;
wherein the magnification is 30000 times.
FIG. 4 is an AFM spectrum of boron nitride nanoplatelets prepared in example 3 of the present invention.
FIG. 5 shows XRD patterns of boron nitride nanoplatelets prepared in examples 1 to 3 of the present invention.
Detailed Description
It should be noted that the following detailed description is illustrative and is intended to provide further explanation of the invention. 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 present invention. As used herein, the singular is also intended to include the plural unless the context clearly indicates otherwise, and furthermore, it is to be understood that the terms "comprises" and/or "comprising" when used in this specification are taken to specify the presence of stated features, steps, operations, devices, components, and/or combinations thereof.
In order to enable those skilled in the art to more clearly understand the technical scheme of the present invention, the technical scheme of the present invention will be described in detail with reference to specific embodiments.
Example 1:
(1) Weighing 0.02mol of zinc nitrate hexahydrate and 0.01mol of sodium borate decahydrate, respectively adding into two beakers with 100mL of deionized water, stirring for 30 minutes in a constant-temperature stirring water bath kettle, and heating to 70 ℃ until the zinc nitrate hexahydrate and the sodium borate decahydrate are completely dissolved;
(2) Pouring the hexahydrate zinc nitrate solution into a stirred sodium borate decahydrate solution at a constant speed, and reacting for 24 hours at 70 ℃;
(3) Centrifugally cleaning the product after the water bath reaction for 3 times, drying at 60 ℃ for more than 10 hours, and collecting to obtain zinc borate nano-sheets;
(4) Carrying out high-temperature reaction on the obtained zinc borate nano-sheet and ammonia gas in a tube furnace, wherein the heating rate is 10 ℃/min, the reaction temperature is 800 ℃, the heat preservation time is 3 hours, and the flow rate of the ammonia gas in the reaction process is 71.9sccm; (5) Adding the product after the high-temperature reaction into hydrochloric acid solution with the concentration of 2mol/L, and carrying out ultrasonic pickling for 4 hours;
(6) And (3) 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 nanosheets.
Example 2:
(1) Weighing 0.02mol of zinc nitrate hexahydrate and 0.01mol of sodium borate decahydrate, respectively adding into two beakers with 100mL of deionized water, stirring for 30 minutes in a constant-temperature stirring water bath kettle, and heating to 70 ℃ until the zinc nitrate hexahydrate and the sodium borate decahydrate are completely dissolved;
(2) Pouring the hexahydrate zinc nitrate solution into a stirred sodium borate decahydrate solution at a constant speed, and reacting for 24 hours at 70 ℃;
(3) Centrifugally cleaning the product after the water bath reaction for 3 times, drying at 60 ℃ for more than 10 hours, and collecting to obtain zinc borate nano-sheets;
(4) Carrying out high-temperature reaction on the mixed powder obtained by the obtained zinc borate nano-sheet and ammonia gas in a tube furnace, wherein the heating rate is 10 ℃/min, the reaction temperature is 900 ℃, the heat preservation time is 3 hours, and the flow rate of the ammonia gas in the reaction process is 71.9sccm;
(5) Adding the product after the high-temperature reaction into hydrochloric acid solution with the concentration of 2mol/L, and carrying out ultrasonic pickling for 4 hours;
(6) And (3) 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 nanosheets.
Example 3:
(1) Weighing 0.02mol of zinc nitrate hexahydrate and 0.01mol of sodium borate decahydrate, respectively adding into two beakers with 100mL of deionized water, stirring for 30 minutes in a constant-temperature stirring water bath kettle, and heating to 70 ℃ until the zinc nitrate hexahydrate and the sodium borate decahydrate are completely dissolved;
(2) Pouring the hexahydrate zinc nitrate solution into a stirred sodium borate decahydrate solution at a constant speed, and reacting for 24 hours at 70 ℃;
(3) Centrifugally cleaning the product after the water bath reaction for 3 times, drying at 60 ℃ for more than 10 hours, and collecting to obtain zinc borate nano-sheets;
(4) Carrying out high-temperature reaction on the mixed powder obtained by the obtained zinc borate nano-sheet and ammonia gas in a tube furnace, wherein the heating rate is 10 ℃/min, the reaction temperature is 1000 ℃, the heat preservation time is 3 hours, and the flow rate of the ammonia gas in the reaction process is 71.9sccm;
(5) Adding the product after the high-temperature reaction into hydrochloric acid solution with the concentration of 2mol/L, and carrying out ultrasonic pickling for 4 hours;
(6) And (3) 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 nanosheets.
Example 4:
(1) Weighing 0.02mol of zinc nitrate hexahydrate and 0.01mol of sodium borate decahydrate, respectively adding into two beakers with 100mL of deionized water, stirring for 30 minutes in a constant-temperature stirring water bath kettle, and heating to 70 ℃ until the zinc nitrate hexahydrate and the sodium borate decahydrate are completely dissolved;
(2) Pouring the hexahydrate zinc nitrate 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 10 hours, and collecting to obtain zinc borate nano-sheets;
(4) Carrying out high-temperature reaction on the mixed powder obtained by the obtained zinc borate nano-sheet and ammonia gas in a tube furnace, wherein the heating rate is 10 ℃/min, the reaction temperature is 900 ℃, the heat preservation time is 3 hours, and the flow rate of the ammonia gas in the reaction process is 71.9sccm;
(5) Adding the product after the high-temperature reaction into hydrochloric acid solution with the concentration of 2mol/L, and carrying out ultrasonic pickling for 4 hours;
(6) And (3) 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 nanosheets.
The above description is only of the preferred embodiments of the present invention and is not intended to limit the present invention, but various modifications and variations can be made to the present invention by those skilled in the art. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (8)
1. The preparation method of the boron nitride nano-sheet is characterized in that the preparation method takes zinc borate nano-sheet as a boron source, and the boron nitride nano-sheet is obtained by heating at high temperature in an ammonia atmosphere;
the boron source is a zinc borate nano-sheet prepared under different reaction conditions, and the zinc borate nano-sheet is simultaneously used as a substrate template for preparing the boron nitride nano-sheet;
the preparation method of the zinc borate nano-sheet comprises the following steps: heating the aqueous solution of zinc nitrate and sodium borate to 65-75 ℃ respectively, mixing the two solutions, and heating in a water bath at 65-75 ℃ for 18-24 hours to prepare the aqueous solution; the concentration of the zinc nitrate solution is 0.2mol/L, and the concentration of the sodium borate solution is 0.1mol/L;
the concrete mode of heating the boron source and ammonia gas at high temperature is as follows: placing a boron source in a tube furnace, introducing ammonia gas to perform high-temperature reaction, wherein the high-temperature reaction temperature is 900-1000 ℃, the heating rate is 8-12 ℃/min, and the heat preservation time is 2-4 h; the method further comprises the step of cleaning and drying the product after the high-temperature heating is finished; the cleaning is carried out by adopting acid liquor.
2. The method for preparing boron nitride nanosheets according to claim 1, wherein after the water bath reaction is finished, the reaction product is washed and dried to obtain the zinc borate nanosheets, and the drying temperature is 55-65 ℃ and the drying time is 8-12 h.
3. The method for preparing boron nitride nanosheets of claim 1, wherein the flow rate of ammonia gas is 70-140 sccm.
4. The method for preparing boron nitride nanosheets of claim 1, wherein the flow rate of ammonia gas is 70-72 sccm.
5. The method of producing boron nitride nanosheets of claim 1, wherein the ammonia gas flow is 71.9sccm.
6. The method for preparing boron nitride nanosheets of claim 1, wherein the acid solution is hydrochloric acid, nitric acid or sulfuric acid solution.
7. The method for preparing boron nitride nanosheets of claim 6, wherein the pickling is carried out by using hydrochloric acid solution, the concentration of hydrochloric acid is 1.5-2.5 mol/L, and the time of ultrasonic cleaning is 3-5 h.
8. The method for preparing boron nitride nanosheets according to claim 7, further comprising a water washing step after ultrasonic washing, wherein deionized water is used for centrifugal washing for 3-5 times, and the boron nitride nanosheets are obtained by drying at 60-80 ℃ for 8-12 h after washing.
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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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| 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 |
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| CN114751387B (en) * | 2022-04-11 | 2023-11-28 | 山东大学 | Method for efficiently preparing boron nitride nanosheets |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| 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 |
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| 高平强等."一步沉淀法合成片状纳米硼酸锌及其性能表征".《纳米技术与精密工程》.2013,第11卷(第2期),第119页左栏第30行-右栏第5行. * |
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