CN110980664B - Porous few-layer h-BN nanosheet and preparation method thereof - Google Patents
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Abstract
The invention relates to a porous few-layer h-BN nanosheet and a preparation method thereof. The technical scheme is as follows: mixing melamine and ammonium chloride, keeping the temperature at 450-650 ℃ in air atmosphere, cleaning and drying to obtain g-C 3 N 4 A material. Adding sodium tetraborate into a container, adding deionized water, stirring under the condition of water bath, and adding g-C under the same condition 3 N 4 And (2) continuously stirring the materials to obtain a mixed solution, transferring the mixed solution into a rotary evaporator for evaporation and concentration, drying, then placing the mixed solution into an alumina crucible, placing the alumina crucible into a high-temperature tubular atmosphere furnace, heating to 500-550 ℃ in an ammonia or nitrogen atmosphere, preserving heat, heating to 1100-1300 ℃, preserving heat, naturally cooling, cleaning and drying to obtain the porous few-layer h-BN nanosheet. The invention has low cost and simple process; the synthesized porous few-layer h-BN nano sheet has the characteristics of controllable structural morphology, high purity, high yield and thinner thickness.
Description
Technical Field
The invention belongs to the technical field of h-BN nanosheets. In particular to a porous few-layer h-BN nano-sheet and a preparation method thereof.
Background
In recent years, with the rapid development of graphene and the maturity of research technology, white graphene-boron nitride is widely concerned by researchers due to its unique structure similar to carbon material and its excellent thermal stability, chemical stability and oxidation resistance. Boron nitride exists in four common crystal forms: hexagonal boron nitride (h-BN), rhombohedral boron nitride (r-BN), cubic boron nitride (c-BN), and wurtzite boron nitride (w-BN). h-BN has received much attention from researchers due to its unique hexagonal layered structure similar to graphite and its excellent properties.
The main preparation methods of h-BN comprise a mechanical stripping method, a solid-phase reaction method, a chemical vapor deposition method, a precursor method and the like, but some methods still have the defects of high raw material danger, high synthesis temperature, high reaction pressure and difficult control of the shape and the size of a product. Such as Shi et al (Shi Y, hamsen C, jia X, et al Synthesis of raw-layer hexagonal boron nitride film by chemical vapor deposition [ J)]Nano Letters,2010,10 (10): 4134-4139.) H-BN films with a thickness of between 5 and 50nm were successfully prepared on nickel substrates using CVD method starting from borazine. However, the size of the prepared film is limited due to the size of the grain boundary on the surface of the metallic nickel, the grain boundary is more, the required raw materials are expensive, and industrial mass production cannot be realized. The template method is widely applied to the preparation of various nano structures because of the advantages of simple experimental device, convenient operation, controllable shape and the like, thereby having great potential for preparing h-BN materials with controllable appearance. Such as the researchers of Michael Rousseas et al (Rousseas M, goldstein A P, mickelson W, et al. Synthesis of Highly Crystalline sp 2 -Bonded Boron Nitride Aerogels[J]ACS Nano,2013,7 (10): 8540-8546.) graphene aerosol is used as a template under flowing nitrogen, and boron nitride aerogel inheriting the macroscopic morphology of the original graphene aerosol is successfully prepared at 1600-1800 ℃, but due to the complex experimental operation, expensive raw materials and high reaction temperature, application limitations still exist, so that the search for a template which is cheap and easy to remove is particularly important. With the development of two-dimensional materials in recent years, the layered structure of h-BN and the adjustable wide forbidden band provide the possibility of modification, so that the preparation method has high specific gravityThe 2D porous h-BN material with the exposed surface area and high surface atoms is more beneficial to modification work such as surface modification, heterojunction construction and the like, thereby obtaining wider application range. Such as Wang et al (Wang X, bando Y, zhi C, et al, boron nitride powders for hydrogen storage [ J ]]Acs Nano,2013,7 (2): 1558-65.) highly porous BN porous micro-strips were successfully prepared by using boric acid and melamine in an ammonia atmosphere, but controllable preparation was still not achieved for 2D porous h-BN nanoplates.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and aims to provide a preparation method of a porous few-layer h-BN nanosheet, which is low in cost and simple in process, and the porous few-layer h-BN nanosheet prepared by the method is controllable in shape and structure, high in purity, high in yield and thin in thickness.
In order to achieve the purpose, the technical scheme adopted by the invention comprises the following specific steps:
step one, g-C 3 N 4 Preparation of (2)
Mixing melamine and ammonium chloride according to the mass ratio of 1: 1-5, and keeping the temperature for 3-4 hours under the conditions of air atmosphere and 450-650 ℃ to obtain a fired material. Then washing the sintered material with deionized water for 3-4 times, and drying at 80-100 ℃ to obtain g-C 3 N 4 A material.
Step two, preparation of h-BN synthetic raw material
Adding sodium tetraborate into a container, adding deionized water into the container according to the mass ratio of the sodium tetraborate to the deionized water of 1: 15-20, stirring for 0.5-1 h under the water bath condition of 85-95 ℃, and then under the same condition, adding the sodium tetraborate to the g-C 3 N 4 The molar ratio of the (C) is 1 to (0.1-0.5), and the g-C is added 3 N 4 And continuously stirring the materials for 0.5 to 1 hour to obtain a mixed solution. And finally, transferring the mixed solution into a rotary evaporator, evaporating at 70-80 ℃ until the mixed solution is 15-20 Vol%, and drying at 80-100 ℃ for 24-32 h to obtain the h-BN synthetic material.
Step three, preparation of porous few-layer h-BN nanosheet
Placing the h-BN synthetic material into an alumina crucible, placing the alumina crucible into a high-temperature tubular atmosphere furnace, heating to 500-550 ℃ at the flow rate of 20-40L/h and the speed of 5-15 ℃/min under the atmosphere of ammonia gas or nitrogen gas, preserving heat for 2-3 h, then continuously heating to 1100-1300 ℃ at the same flow rate and speed, and preserving heat for 3-4 h; and then naturally cooling under the protection of ammonia gas or nitrogen gas atmosphere to obtain a fired material. And washing the sintered material with deionized water for 3-4 times, and drying at 80-100 ℃ for 12-15 h to obtain the porous few-layer h-BN nanosheet.
The purity of the melamine is more than or equal to 99 percent.
The purity of the ammonium chloride is more than or equal to 99.5 percent.
The purity of the sodium tetraborate is more than or equal to 99%.
Due to the adoption of the technical scheme, compared with the prior art, the invention has the following positive effects:
1. the invention takes g-C 3 N 4 The material is a template to synthesize porous few-layer h-BN nanosheets, so that the cost is low and the process is simple; the melamine, ammonium chloride and sodium tetraborate are cheap and non-toxic, so the method is environment-friendly and suitable for industrial production.
2. In the invention, g-C 3 N 4 The porous few-layer h-BN nanosheet synthesized by using the material as the template has the characteristics of controllable morphological structure, high purity, high yield and thinner thickness.
g-C as template in the invention 3 N 4 The material can form 2D nano-sheets in the secondary heat treatment process, so that the material can be used as a template for the growth of the 2D h-BN nano-sheets; g-C as sacrificial template 3 N 4 The material can form gas substances to be volatilized in the synthesis process, so that the formation of a porous structure is promoted; g-C 3 N 4 The material exists as a sacrificial template, and no other impurities are introduced, so that the purity of the prepared porous few-layer h-BN nanosheet is ensured; analogous to carbothermic processes, g-C 3 N 4 Carbon in the material has a promoting effect on the reaction, so that the reaction is more complete, and the prepared porous few-layer h-BN sodium is ensuredHigh yield of rice flakes.
In the invention, g-C 3 N 4 Detecting a porous few-layer h-BN nano sheet synthesized by taking the material as a template: the specific surface area is 150 to 200m 2 ·g -1 (ii) a The total pore volume is 0.4-0.5 cm 3 ·g -1 (ii) a The average pore diameter is 2-10 nm; the average thickness is 4-5 nm.
The invention has low cost and simple process; the synthesized porous few-layer h-BN nanosheet has the characteristics of controllable structural morphology, high purity, high yield and thinner thickness.
Drawings
FIG. 1 is an XRD pattern of a porous few-layer h-BN nanosheet prepared in accordance with the present invention;
FIG. 2 is an SEM image of the porous few-layer h-BN nanoplates shown in FIG. 1;
FIG. 3 is a pore size distribution plot of the porous few-layer h-BN nanoplates shown in FIG. 1;
FIG. 4 is an AFM image of the porous few-layered h-BN nanoplates shown in FIG. 1.
Detailed Description
The invention is further described with reference to the following figures and detailed description, without limiting the scope of the invention.
Step one, g-C 3 N 4 Preparation of
Mixing melamine and ammonium chloride according to the mass ratio of 1: 1-5, and keeping the temperature for 3-4 h under the conditions of air atmosphere and 450-650 ℃ to obtain a fired material. Then washing the sintered material with deionized water for 3-4 times, and drying at 80-100 ℃ to obtain g-C 3 N 4 A material.
Step two, preparation of h-BN synthetic raw material
Adding sodium tetraborate into a container, adding deionized water into the container according to the mass ratio of the sodium tetraborate to the deionized water of 1: 15-20, stirring for 0.5-1 h under the condition of water bath at 85-95 ℃, and then under the same condition, adding the sodium tetraborate to the g-C 3 N 4 The molar ratio of the (C) is 1 to (0.1-0.5), and the g-C is added 3 N 4 Continuously stirring the materials for 0.5cAnd (5) obtaining a mixed solution after 1 h. And finally, transferring the mixed solution into a rotary evaporator, evaporating at 70-80 ℃ until the mixed solution is 15-20 Vol%, and drying at 80-100 ℃ for 24-32 h to obtain the h-BN synthetic material.
Step three, preparation of porous few-layer h-BN nanosheet
Placing the h-BN synthetic material into an alumina crucible, placing the alumina crucible into a high-temperature tubular atmosphere furnace, heating to 500-550 ℃ at the flow rate of 20-40L/h and the speed of 5-15 ℃/min under the atmosphere of ammonia gas or nitrogen gas, preserving heat for 2-3 h, then continuously heating to 1100-1300 ℃ at the same flow rate and speed, and preserving heat for 3-4 h; and then naturally cooling under the protection of ammonia gas or nitrogen gas atmosphere to obtain a fired material. And washing the sintered material with deionized water for 3-4 times, and drying at 80-100 ℃ for 12-15 h to obtain the porous few-layer h-BN nanosheet.
In this embodiment: the purity of the melamine is more than or equal to 99 percent; the purity of the ammonium chloride is more than or equal to 99.5 percent; the purity of the sodium tetraborate is more than or equal to 99%. The detailed description is omitted in the embodiments.
Example 1
A porous few-layer h-BN nanosheet and a preparation method thereof. The preparation method comprises the following specific steps:
step one, g-C 3 N 4 Preparation of
Mixing melamine and ammonium chloride according to the mass ratio of 1: 1, and keeping the temperature for 4 hours at 450 ℃ in the air atmosphere to obtain a fired material. Washing the fired material with deionized water for 4 times, and drying at 80 deg.C to obtain g-C 3 N 4 A material.
Step two, preparation of h-BN synthetic raw material
Adding sodium tetraborate into a container, adding deionized water into the container according to the mass ratio of 1: 15 of sodium tetraborate to deionized water, stirring for 1h under the condition of water bath at 85 ℃, and then under the same condition, adding sodium tetraborate to the g-C 3 N 4 Is added in the g-C with the molar ratio of 1: 0.1 3 N 4 The materials are continuously stirred for 1 hour,a mixed solution was obtained. And finally, transferring the mixed solution into a rotary evaporator, evaporating at 80 ℃ until the volume of the mixed solution is 15Vol%, and drying at 80 ℃ for 32h to obtain the h-BN synthetic material.
Step three, preparation of porous few-layer h-BN nanosheet
Placing the h-BN synthetic material in an alumina crucible, placing the alumina crucible in a high-temperature tubular atmosphere furnace, heating to 500 ℃ at the flow rate of 40L/h and the speed of 15 ℃/min under the nitrogen atmosphere, preserving heat for 2h, then continuously heating to 1100 ℃ at the same flow rate and speed, and preserving heat for 4h; and then naturally cooling under the protection of ammonia gas or nitrogen gas atmosphere to obtain a fired material. And washing the sintered material with deionized water for 3 times, and drying at 80 ℃ for 12 hours to obtain the porous few-layer h-BN nanosheet.
Example 2
A porous few-layer h-BN nanosheet and a preparation method thereof. The preparation method comprises the following specific steps:
step one, g-C 3 N 4 Preparation of
Mixing melamine and ammonium chloride according to the mass ratio of 1: 2, and keeping the temperature for 3.5 hours under the conditions of air atmosphere and 600 ℃ to obtain a fired material. Washing the fired material with deionized water for 4 times, and drying at 85 deg.C to obtain g-C 3 N 4 A material.
Step two, preparation of h-BN synthetic raw material
Adding sodium tetraborate into a container, adding deionized water into the container according to the mass ratio of the sodium tetraborate to the deionized water of 1: 16, stirring for 0.8h under the water bath condition of 90 ℃, and then under the same condition, adding sodium tetraborate to the g-C 3 N 4 Is added with the g-C in a molar ratio of 1: 0.3 3 N 4 The materials were stirred for 0.8h to obtain a mixed solution. And finally, transferring the mixed solution into a rotary evaporator, evaporating at 78 ℃ until the mixed solution is 17Vol%, and drying at 85 ℃ for 28 hours to obtain the h-BN synthetic material.
Step three, preparation of porous few-layer h-BN nanosheet
Placing the h-BN synthetic material in an alumina crucible, placing the alumina crucible in a high-temperature tubular atmosphere furnace, heating to 520 ℃ at the flow rate of 35L/h and the speed of 12 ℃/min under the atmosphere of ammonia gas, preserving heat for 2.4h, then continuously heating to 1200 ℃ at the same flow rate and speed, and preserving heat for 3.8h; and then naturally cooling under the protection of ammonia gas or nitrogen gas atmosphere to obtain a fired material. And washing the sintered material with deionized water for 3 times, and drying at 85 ℃ for 13 hours to obtain the porous few-layer h-BN nanosheet.
Example 3
A porous few-layer h-BN nanosheet and a preparation method thereof. The preparation method comprises the following specific steps:
step one, g-C 3 N 4 Preparation of
Mixing melamine and ammonium chloride according to the mass ratio of 1: 4, and keeping the temperature for 3 hours at 650 ℃ in an air atmosphere to obtain a fired material. Washing the sintered material with deionized water for 3 times, and drying at 90 deg.C to obtain g-C 3 N 4 A material.
Step two, preparation of h-BN synthetic raw material
Adding sodium tetraborate into a container, adding deionized water into the container according to the mass ratio of 1: 18 of sodium tetraborate to deionized water, stirring for 0.6h under the water bath condition of 90 ℃, and then under the same condition, adding sodium tetraborate to the g-C 3 N 4 Is added in the g-C with the molar ratio of 1: 0.4 3 N 4 The materials were stirred for 0.6h to obtain a mixed solution. And finally, transferring the mixed solution into a rotary evaporator, evaporating at 75 ℃ until the volume of the mixed solution is 18Vol%, and drying at 90 ℃ for 26h to obtain the h-BN synthetic material.
Step three, preparation of porous few-layer h-BN nanosheet
Placing the h-BN synthetic material in an alumina crucible, placing the alumina crucible in a high-temperature tubular atmosphere furnace, heating to 540 ℃ at the flow rate of 30L/h and the speed of 8 ℃/min under the nitrogen atmosphere, preserving heat for 2.8h, then continuously heating to 1300 ℃ at the same flow rate and speed, and preserving heat for 3.5h; and then naturally cooling under the protection of ammonia gas or nitrogen gas atmosphere to obtain a fired material. And washing the sintered material with deionized water for 4 times, and drying for 14 hours at 90 ℃ to obtain the porous few-layer h-BN nanosheet.
Example 4
A porous few-layer h-BN nanosheet and a preparation method thereof. The preparation method comprises the following specific steps:
step one, g-C 3 N 4 Preparation of
Mixing melamine and ammonium chloride according to the mass ratio of 1: 5, and keeping the temperature for 3 hours at 550 ℃ in the air atmosphere to obtain a fired material. Cleaning the fired material with deionized water for 3 times, and drying at 100 ℃ to obtain g-C 3 N 4 A material.
Step two, preparation of h-BN synthetic raw material
Adding sodium tetraborate into a container, adding deionized water into the container according to the mass ratio of 1: 20 of the sodium tetraborate to the deionized water, stirring for 0.5h under the water bath condition of 95 ℃, and then under the same condition, adding the sodium tetraborate to the g-C 3 N 4 Is added in the g-C with the molar ratio of 1: 0.5 3 N 4 The materials were stirred for 0.5h to obtain a mixed solution. And finally, transferring the mixed solution into a rotary evaporator, evaporating at 70 ℃ until the volume of the mixed solution is 20Vol%, and drying at 100 ℃ for 24h to obtain the h-BN synthetic material.
Step three, preparation of porous few-layer h-BN nanosheet
Placing the h-BN synthetic material in an alumina crucible, placing the alumina crucible in a high-temperature tubular atmosphere furnace, heating to 550 ℃ at the flow rate of 20L/h and the speed of 5 ℃/min under the atmosphere of ammonia gas, preserving heat for 3h, then continuously heating to 1200 ℃ at the same flow rate and speed, and preserving heat for 3h; and then naturally cooling under the protection of ammonia gas or nitrogen gas atmosphere to obtain a fired material. And washing the sintered material with deionized water for 4 times, and drying for 15 hours at 100 ℃ to obtain the porous few-layer h-BN nanosheet.
Compared with the prior art, the specific implementation mode has the following positive effects:
1. in the invention, g-C 3 N 4 The material is a template to synthesize porous few-layer h-BN nanosheets, so that the cost is low and the process is simple; the adopted melamine, ammonium chloride and sodium tetraborate are cheap and non-toxic, so the method is environment-friendly and is suitable for industrial production.
2. In the invention, g-C 3 N 4 The porous few-layer h-BN nanosheet synthesized by using the material as the template has the characteristics of controllable morphological structure, high purity, high yield and thinner thickness.
g-C as template in the invention 3 N 4 The material can form 2D nano-sheets in the secondary heat treatment process, so that the material can be used as a template for the growth of the 2D h-BN nano-sheets; g-C as sacrificial template 3 N 4 The material can form gas substances to be volatilized in the synthesis process, so that the formation of a porous structure is promoted; g-C 3 N 4 The material exists as a sacrificial template, and no other impurities are introduced, so that the purity of the prepared porous few-layer h-BN nanosheet is ensured; analogous to carbothermic processes, g-C 3 N 4 Carbon in the material has a promoting effect on the reaction, so that the reaction is more complete, and the high yield of the prepared porous few-layer h-BN nanosheet is ensured.
3. The porous few-layer h-BN nanosheet prepared by the specific embodiment is shown in the attached drawing: fig. 1 is an XRD pattern of porous few-layer h-BN nanosheets prepared in example 4; FIG. 2 is an SEM image of the porous few-layer h-BN nanoplates shown in FIG. 1; FIG. 3 is a pore size distribution diagram of the porous few-layer h-BN nanoplates shown in FIG. 1; FIG. 4 is an AFM image of the porous few-layer h-BN nanoplates shown in FIG. 1. As can be seen from fig. 1: g-C 3 N 4 The material is a sacrificial template, and the prepared porous few-layer h-BN nanosheet is high in purity and crystallinity; as can be seen from fig. 2: the micro-morphology of the prepared porous few-layer h-BN nanosheet is a spongy porous structure; as can be seen from fig. 3: the aperture of the prepared porous few-layer h-BN nano sheet is distributed to 2-10 nm; as can be seen from fig. 4: the thickness of the prepared porous few-layer h-BN nano sheet is 4-5 nm. As can be seen from the drawings: the prepared porous few-layer h-BN nanosheet is controllable in morphology structure, so that the porous few-layer h-BN nanosheet is obtainedThe obtained spongy porous structure can effectively improve the specific surface area.
The porous few-layer h-BN nanosheet prepared by the specific embodiment is detected: the specific surface area is 150 to 200m 2 ·g -1 (ii) a The total pore volume is 0.4-0.5 cm 3 ·g -1 (ii) a The average pore diameter is 2-10 nm; the average thickness is 4-5 nm.
The invention has low cost and simple process; the synthesized porous few-layer h-BN nanosheet has the characteristics of controllable structural morphology, high purity, high yield and thinner thickness.
Claims (4)
1. A preparation method of a porous few-layer h-BN nanosheet is characterized by comprising the following specific steps:
step one, g-C 3 N 4 Preparation of
Mixing melamine and ammonium chloride according to the mass ratio of 1: 1-5, and keeping the temperature for 3-4 h at 450-650 ℃ in an air atmosphere to obtain a fired material; then washing the sintered material with deionized water for 3-4 times, and drying at 80-100 ℃ to obtain g-C 3 N 4 A material;
step two, preparation of h-BN synthetic raw material
Adding sodium tetraborate into a container, adding deionized water into the container according to the mass ratio of the sodium tetraborate to the deionized water of 1: 15-20, stirring for 0.5-1 h under the condition of water bath at 85-95 ℃, and then under the same condition, adding the sodium tetraborate to the g-C 3 N 4 The molar ratio of the (C) is 1 to (0.1-0.5), and the g-C is added 3 N 4 Continuously stirring the materials for 0.5 to 1 hour to obtain a mixed solution; finally, the mixed solution is moved into a rotary evaporator, is evaporated to 15-20 Vol% under the condition of 70-80 ℃, and is dried for 24-32 h under the condition of 80-100 ℃ to obtain h-BN synthetic material;
step three, preparation of porous few-layer h-BN nanosheet
Placing the h-BN synthetic material into an alumina crucible, placing the alumina crucible into a high-temperature tubular atmosphere furnace, heating to 500-550 ℃ at the flow rate of 20-40L/h and the speed of 5-15 ℃/min under the atmosphere of ammonia gas or nitrogen gas, preserving heat for 2-3 h, then continuously heating to 1100-1300 ℃ at the same flow rate and speed, and preserving heat for 3-4 h; then naturally cooling under the protection of ammonia or nitrogen atmosphere to obtain a fired material; and washing the sintered material with deionized water for 3-4 times, and drying at 80-100 ℃ for 12-15 h to obtain the porous few-layer h-BN nanosheet.
2. The preparation method of the porous few-layer h-BN nanosheet according to claim 1, wherein the purity of the melamine is greater than or equal to 99%.
3. The preparation method of the porous few-layer h-BN nanosheet according to claim 1, wherein the purity of the ammonium chloride is greater than or equal to 99.5%.
4. The preparation method of the porous few-layer h-BN nano sheet according to claim 1, wherein the purity of the sodium tetraborate is not less than 99%.
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| CN111483983B (en) * | 2020-05-06 | 2021-08-03 | 河北工业大学 | Preparation method of hexagonal boron nitride nanosphere with layered cavitation structure |
| CN111531181B (en) * | 2020-05-11 | 2022-12-16 | 中国科学院重庆绿色智能技术研究院 | Preparation method of high-performance porous honeycomb tin-carbon lithium battery cathode material |
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