CN115448264A - Preparation method of porous boron nitride nanosheet - Google Patents
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- CN115448264A CN115448264A CN202211054828.6A CN202211054828A CN115448264A CN 115448264 A CN115448264 A CN 115448264A CN 202211054828 A CN202211054828 A CN 202211054828A CN 115448264 A CN115448264 A CN 115448264A
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Abstract
The invention relates to a preparation method of a porous boron nitride nanosheet. Firstly, synthesizing nano flaky zinc borate as a boron source and a substrate template, and ammonia gas as a nitrogen source, so as to prepare porous boron nitride nanosheets which are good in appearance and have micron-sized transverse dimensions at a lower temperature; meanwhile, the nano flaky zinc borate template is prepared by adopting a one-step precipitation method, so that the yield is high, the operation is simple, the porous boron nitride nanosheet prepared by the method has the advantages of high yield and mass production, and a foundation is provided for the mass application of the porous 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 porous boron nitride nanosheet.
Background
The information in this background section is only for enhancement of understanding of the general background of the invention and is not necessarily to be construed as an admission or any form of suggestion that this information forms the prior art that is already known to a person of ordinary skill in the art.
In recent years, the preparation and application of boron nitride nanosheets attract extensive attention of researchers, and the boron nitride nanosheets have excellent mechanical properties, thermal properties, chemical stability and unique dielectric properties and electrical insulation properties. However, most of the existing preparation methods of boron nitride nanosheets still have the defects of low yield, and even some methods have considerable yield, the defects of harsh and complex preparation conditions and the like.
The chemical vapor deposition method is the most promising method for preparing boron nitride nanosheets, and is divided into a template-free method and a template method. The template method is always a hotspot method for preparing the boron nitride nanosheet due to the advantages of controllable appearance and mass production. The method is mainly limited to the selection and synthesis of the template, and finding an excellent flaky template often plays a crucial role in the preparation of the boron nitride nanosheet. Therefore, the research on a simple and large-scale new method for preparing the porous boron nitride nanosheet and the reaction template is still a research hotspot in the field.
Disclosure of Invention
Based on the technical background, the invention aims to provide an efficient preparation method of porous boron nitride nanosheets. In order to achieve the technical purpose, the invention provides a method for efficiently preparing a large amount of zinc borate flaky templates by a one-step precipitation method of a zinc nitrate hexahydrate solution and a sodium borate decahydrate solution, which provides a boron source and a substrate template for preparing porous boron nitride nanosheets by a chemical vapor deposition method, uses ammonia gas as a nitrogen source, and obtains the porous boron nitride nanosheets by the steps of high-temperature reaction, acid washing, centrifugation, drying, collection and the like. The preparation method has the advantages of stability, reliability, simple operation, lower equipment cost, easily obtained raw materials and high yield.
In a first aspect of the invention, a preparation method of a porous boron nitride nanosheet is provided; the preparation method comprises the following steps:
(1) Preparing a sodium borate decahydrate solution and a zinc nitrate hexahydrate solution, respectively stirring and dispersing the two solutions until the two solutions are completely dissolved, then mixing the two solutions, carrying out water bath reaction, and washing and drying the mixture to obtain a zinc borate sheet-shaped substrate template;
(2) And (3) placing the zinc borate sheet substrate template in an ammonia atmosphere for high-temperature nitridation to prepare the porous boron nitride nanosheet.
Furthermore, the concentration of the zinc nitrate hexahydrate solution is 0.1-0.4 mol/L.
Further, the concentration of the sodium borate decahydrate solution is 0.05-0.2 mol/L.
Further, in the step (1), the temperature is room temperature (20 ℃ to 30 ℃) when stirring and dispersing, and the stirring time is more than 30 min.
Further, an aqueous solution of zinc nitrate hexahydrate was poured into an aqueous solution of sodium borate decahydrate in a stirred state by a pouring method.
Furthermore, the water bath reaction temperature is 70-80 ℃, and the reaction time is 21-24 h.
Further, after the water bath reaction is finished, washing the reaction product for 3-5 times in a centrifugal mode, and drying to obtain the zinc borate nanosheet, wherein the centrifugal speed is 4000-5000 r/min, the drying temperature is 60-90 ℃, and the drying time is 8-16 h.
Preferably, the boron source and ammonia gas are heated at high temperature in the following specific manner: placing the zinc borate sheet-shaped substrate template in a tubular furnace, vacuumizing the tubular furnace, and introducing argon as protective gas into the tubular furnace; and then setting a heating program, closing argon protective gas after heating, and introducing ammonia gas into a tubular furnace to perform high-temperature reaction, wherein the reaction temperature is 1000 ℃, the heating rate is 5-15 ℃/min, and the heat preservation time is 2-4 h.
Further, the flow rate of the argon gas is 50-200 sccm.
Further, the flow rate of the ammonia gas is 60-90 sccm; further, it is 70 to 75sccm, and a specific example is 71.9sccm.
Preferably, the method also 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 solution.
Further, hydrochloric acid solution is adopted for ultrasonic cleaning in the acid cleaning process, the concentration of hydrochloric acid is 2-5 mol/L, and the time of ultrasonic cleaning is 3-5 h.
The ultrasonic cleaning method further comprises a water cleaning step, wherein deionized water is adopted for centrifugal cleaning, the cleaning frequency can be adjusted according to the cleaning effect, for example, 3-5 times are carried out, the centrifugal rotating speed is 4000-5000 r/min, and after the cleaning is finished, the porous boron nitride nanosheet is obtained by drying for 8-16 h at 60-100 ℃.
In a second aspect of the invention, a porous boron nitride nanosheet prepared by the preparation method is provided.
The transverse size of the zinc borate nanosheet template prepared in the above manner is 1-5 microns, and the preparation method adopting a one-step precipitation method has the advantages of simplicity and high yield, and provides basic conditions for efficiently preparing a large amount of porous boron nitride nanosheets; in addition, the thickness of the porous boron nitride nanosheet prepared in the manner is 3-15nm, the transverse size of the porous boron nitride nanosheet is basically consistent with that of a zinc borate slice mounting template, the porous boron nitride nanosheet has the advantage of being capable of being produced in a large scale, and the single-time yield can reach gram level.
The invention has the beneficial effects that:
1. the invention provides a method for preparing a large amount of zinc borate nanosheets, and the prepared zinc borate nanosheets are used as a boron source and a reaction template for preparing porous boron nitride nanosheets, so that a foundation is provided for efficiently preparing the porous boron nitride nanosheets in a large amount.
2. The preparation method of the porous boron nitride nanosheet provided by the invention can realize mass preparation of the porous 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 porous boron nitride nanosheet.
3. The preparation method provided by the invention has the advantages of easily available raw materials, low cost, relatively simple production equipment, convenience in operation and easiness in realizing industrial expanded production.
Drawings
The accompanying drawings, which are incorporated in and constitute a part of this application, illustrate embodiments of the application and, together with the description, serve to explain the application and are not intended to limit the application.
FIG. 1 is a scanning electron micrograph of zinc borate sheet-like substrate template prepared by water bath reaction for 24h in example 1 of the present invention at different magnifications.
FIG. 2 is an XRD pattern of a zinc borate flake substrate template prepared by 24h water bath reaction in example 1 of the present invention.
Fig. 3 is a scanning electron microscope photograph of the porous boron nitride nanosheet prepared in example 1 of the present invention at different magnifications.
Fig. 4 is an XRD spectrum of the porous boron nitride nanosheet prepared in example 1 of the present invention.
Fig. 5 is a transmission electron microscope photograph of porous boron nitride nanosheets prepared in example 1 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.
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, and stirring the mixture in a constant-temperature stirring water bath kettle for more than 30 minutes 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 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 obtained zinc borate nanosheet and ammonia gas in a tubular furnace, vacuumizing the tubular furnace before heating, then introducing argon gas as protective atmosphere, starting heating, then introducing ammonia gas, closing argon gas, wherein the heating rate in the heating process is 10 ℃/min, the reaction temperature is 1000 ℃, the heat preservation time is 3h, and the flow of ammonia gas in the reaction process is 71.9sccm;
(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 ultrasonically-acid-washed suspension by using deionized water (the rotating speed is 4000 r/min) for 3 times, drying at 60 ℃ for more than 10h, and collecting to obtain the boron nitride nanosheet.
FIG. 1 is a scanning electron micrograph of a zinc borate sheet-like substrate template prepared in example 1 by water bath reaction for 24h at different magnifications; the size of the sheet-shaped substrate template is about 1-5 microns according to a scanning electron micrograph; wherein, the magnification of fig. 1A is 2500 times; the magnification of fig. 1B is 5000 times.
FIG. 2 is an XRD pattern of a zinc borate flake substrate template prepared by a water bath reaction for 24 hours in example 1 of the present invention. As can be seen from fig. 2, the resulting product was zinc borate.
FIG. 3 is a scanning electron microscope photograph of porous boron nitride nanosheets prepared in example 1 of the present invention at different magnifications; from the figure, the prepared porous boron nitride nanosheet has more pores on the surface. Wherein the magnification of fig. 3A is 20000 times; the magnification of fig. 3B is 40000 times.
FIG. 4 is an XRD spectrum of porous boron nitride nanosheets prepared in example 1 of the present invention; as can be seen from the figure, the characteristic peak of the prepared porous boron nitride nanosheet corresponds to the peak of h-BN, and no hetero-phase exists.
Fig. 5 is a transmission electron microscope photograph of porous boron nitride nanosheets prepared in example 1 of the present invention; wherein, fig. 5A is a low-power transmission electron microscope photograph of the porous boron nitride nanosheet, in which it can be clearly observed that a large number of pores exist on the surface of the boron nitride nanosheet; FIG. 5B is a high-power transmission electron microscope photograph of the side surface of the prepared porous boron nitride nanosheet, from which it can be observed that the thickness of the nanosheet is 3.64nm, and the number of layers is 11, which proves that the prepared porous boron nitride nanosheet is relatively thin.
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, and stirring the mixture in a constant-temperature stirring water bath kettle for more than 30 minutes 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 21 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, vacuumizing the tubular furnace before heating, introducing argon gas as a protective atmosphere, starting heating, introducing ammonia gas, closing argon gas, wherein the heating rate in the heating process is 10 ℃/min, the reaction temperature is 1000 ℃, the heat preservation time is 3h, and the flow of ammonia gas in the reaction process is 71.9sccm;
(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 ultrasonically-acid-washed suspension by using deionized water (the rotating speed is 5000 r/min) for 3 times, drying at 60 ℃ for more than 10h, and collecting to obtain the boron nitride nanosheet.
Example 3:
(1) Weighing 0.04mol of zinc nitrate hexahydrate and 0.02mol of sodium borate decahydrate, respectively adding the zinc nitrate hexahydrate and the sodium borate decahydrate into two beakers filled with 100mL of deionized water, and stirring the mixture in a constant-temperature stirring water bath kettle for more than 30 minutes 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 21 hours at 80 ℃;
(3) Centrifuging the product after the water bath reaction (the centrifugal rotation speed is 4000 r/min), cleaning for 5 times, drying for 8 hours at 90 ℃, 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, vacuumizing the tubular furnace before heating, introducing argon gas as a protective atmosphere, starting heating, introducing ammonia gas, closing argon gas, wherein the heating rate in the heating process is 15 ℃/min, the reaction temperature is 1000 ℃, the heat preservation time is 4h, and the flow of ammonia gas in the reaction process is 71.9sccm;
(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 5 hours;
(6) And (3) centrifugally cleaning the ultrasonically acid-washed suspension by using deionized water (the rotating speed is 5000 r/min) for 3 times, drying at 60 ℃ for more than 10h, and collecting to obtain the boron nitride nanosheet.
Example 4:
(1) Weighing 0.01mol of zinc nitrate hexahydrate and 0.005mol of sodium borate decahydrate, respectively adding the zinc nitrate hexahydrate and the sodium borate decahydrate into two beakers filled with 100mL of deionized water, and stirring the mixture in a constant-temperature stirring water bath kettle for more than 30 minutes 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 21 hours at 75 ℃;
(3) Centrifuging the product after the water bath reaction (the centrifugal rotating speed is 4000 r/min), cleaning for 5 times, drying at 90 ℃ for 8h, 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, vacuumizing the tubular furnace before heating, then introducing argon gas as protective atmosphere, starting heating, then introducing ammonia gas, closing argon gas, wherein the heating rate in the heating process is 15 ℃/min, the reaction temperature is 1000 ℃, the heat preservation time is 4h, and the flow of ammonia gas in the reaction process is 71.9sccm;
(5) Adding the product after the high-temperature reaction into a hydrochloric acid solution with the concentration of 2mol/L for ultrasonic acid washing for 5 hours;
(6) And centrifugally cleaning the ultrasonically-acid-washed suspension by using deionized water (the rotating speed is 5000 r/min) for 3 times, drying at 60 ℃ for more than 10h, and collecting to obtain the boron nitride nanosheet.
The above description is only a preferred embodiment of the present application and is not intended to limit the present application, 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 application shall be included in the protection scope of the present application.
Claims (10)
1. A preparation method of a porous boron nitride nanosheet is characterized by comprising the following steps:
(1) Preparing a sodium borate decahydrate solution and a zinc nitrate hexahydrate solution, respectively stirring and dispersing the two solutions until the two solutions are completely dissolved, then mixing the two solutions, carrying out water bath reaction, and washing and drying the mixture to obtain a zinc borate sheet-shaped substrate template;
(2) And (3) placing the zinc borate sheet substrate template in an ammonia atmosphere for high-temperature nitridation to prepare the porous boron nitride nanosheet.
2. The preparation method according to claim 1, wherein the concentration of the zinc nitrate hexahydrate solution is 0.1 to 0.4mol/L; the concentration of the sodium borate decahydrate solution is 0.05-0.2 mol/L.
3. The process according to claim 1, wherein the temperature in the step (1) is room temperature (20 to 30 ℃) and the stirring time is 30min or more.
4. The production method according to claim 1, wherein the aqueous solution of zinc nitrate hexahydrate is poured into the aqueous solution of sodium borate decahydrate in a stirred state by a pouring method.
5. The preparation method of claim 1, wherein the water bath reaction temperature is 70-80 ℃ and the reaction time is 21-24 h.
6. The preparation method of the zinc borate nanosheet according to claim 1, wherein after the water bath reaction is finished, the reaction product is washed for 3 to 5 times in a centrifugal mode and dried to obtain the zinc borate nanosheet, the centrifugal rotation speed is 4000 to 5000r/min, the drying temperature is 60 to 90 ℃, and the drying time is 8 to 16 hours.
7. The preparation method according to claim 1, wherein the boron source and ammonia gas are heated at high temperature in the following specific manner: placing the zinc borate sheet-shaped substrate template in a tubular furnace, vacuumizing the tubular furnace, and introducing argon gas into the tubular furnace as protective gas; then setting a heating program, closing argon protective gas after heating, and introducing ammonia gas into a tubular furnace to perform high-temperature reaction, wherein the reaction temperature is 1000 ℃, the heating rate is 5-15 ℃/min, and the heat preservation time is 2-4 h; preferably, the flow rate of the argon is 50-200 sccm; preferably, the flow rate of the ammonia gas is 60-90 sccm; more preferably 70 to 75sccm, and still more preferably 71.9sccm.
8. The preparation method according to claim 1, further comprising the steps of cleaning and drying the product after the high temperature nitridation is completed; the cleaning is carried out by adopting acid liquor, and the acid liquor is hydrochloric acid solution.
9. The preparation method of claim 8, wherein the acid washing is carried out by ultrasonic cleaning with hydrochloric acid solution, the hydrochloric acid concentration is 2-5 mol/L, and the ultrasonic cleaning time is 3-5 h; and the ultrasonic cleaning step also comprises a water washing step, wherein deionized water is adopted for centrifugal cleaning, the cleaning frequency is 3-5 times, the centrifugal rotating speed is 4000-5000 r/min, and the porous boron nitride nanosheet is obtained by drying for 8-16 h at 60-100 ℃ after the cleaning is finished.
10. Porous boron nitride nanosheets produced by the method of production according to any one of the preceding claims.
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