CN110577226A - Preparation method of boron nitride/boron phosphate sandwich type hollow sphere - Google Patents
Preparation method of boron nitride/boron phosphate sandwich type hollow sphere Download PDFInfo
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- CN110577226A CN110577226A CN201910991446.8A CN201910991446A CN110577226A CN 110577226 A CN110577226 A CN 110577226A CN 201910991446 A CN201910991446 A CN 201910991446A CN 110577226 A CN110577226 A CN 110577226A
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- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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- 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
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- 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
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- C01P2004/00—Particle morphology
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- C01P2004/03—Particle morphology depicted by an image obtained by SEM
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- C01P2004/30—Particle morphology extending in three dimensions
- C01P2004/32—Spheres
- C01P2004/34—Spheres hollow
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- C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
Abstract
The invention discloses a preparation method of a boron nitride/boron phosphate sandwich type hollow sphere, and belongs to the technical field of material science. The invention provides a preparation method of a boron nitride/boron phosphate sandwich type hollow sphere, which comprises the steps of utilizing self-assembly and Oswald curing effects, annealing at high temperature in air to successfully obtain a boron phosphate hollow sphere structure, then annealing at high temperature in an ammonia atmosphere to grow a layer of boron nitride on the inner surface and the outer surface of the boron phosphate hollow sphere respectively to form a sandwich-like hollow sphere structure. The method is simple, is beneficial to large-scale industrial production, and has remarkable economic and social benefits.
Description
Technical Field
The invention belongs to the technical field of material science, and particularly relates to a preparation method of a boron nitride/boron phosphate sandwich type hollow sphere.
Background
The structure of the material determines its properties and applications. The hollow spherical structure under the micro-nano scale has the properties of low density, large specific surface area, higher load capacity and the like, and the modifiable surface of the hollow spherical structure can improve the performance of the hollow spherical structure in specific application again. Hollow spheres with a particular structure have particular advantages in some specific applications. For example, energy storage, biopharmaceuticals, sensors, and catalysis. In order to obtain better performance, active substances are often added to functionalize the hollow spheres to obtain the hollow sphere composite material. The material with the sandwich structure has the characteristic of utilizing the surface of the carrier to a greater extent, and is a composite material structure with excellent performance. Therefore, the development of the sandwich type hollow sphere composite structure has important significance in developing the performance of the material.
The boron phosphate hollow sphere is obtained by using boron oxide, diammonium phosphate and ammonia as raw materials and adopting a simple self-assembly template-free one-step annealing method. Then, annealing at high temperature in the atmosphere of ammonia gas, and growing a layer of boron nitride on the inner surface and the outer surface of the boron phosphate hollow sphere respectively to form a hollow sphere structure similar to a sandwich. The method is simple and convenient to operate, low in cost, has a large-scale commercial production prospect, and has reference significance for preparation of other sandwich hollow sphere composite materials.
Disclosure of Invention
The invention aims to provide a simple, high-efficiency and low-cost method for preparing a boron nitride/boron phosphate sandwich type hollow sphere composite material. The preparation method has reference significance for the preparation of other sandwich hollow sphere composite materials.
In order to achieve the purpose, the invention adopts the following technical scheme:
A preparation method of a boron nitride/boron phosphate sandwich hollow sphere comprises the steps of taking boron oxide, diammonium hydrogen phosphate and ammonia gas as raw materials, firstly reacting the boron oxide and the diammonium hydrogen phosphate in one step to generate the boron phosphate hollow sphere, then annealing the boron phosphate hollow sphere at a high temperature in an ammonia gas atmosphere, and growing a layer of boron nitride on the inner surface and the outer surface of the boron phosphate hollow sphere to form the boron nitride/boron phosphate sandwich hollow sphere.
A preparation method of a boron nitride/boron phosphate sandwich type hollow sphere comprises the following steps:
(1) Uniformly grinding boron oxide and diammonium hydrogen phosphate according to a certain proportion, and transferring the mixture into a crucible;
(2) The crucible is placed in a tube furnace, the temperature is controlled by program, and the heating rate is 5oC/min, annealing at a certain temperature for a period of time, naturally cooling, washing with water, and drying to obtain the boron phosphate hollow sphere.
(3) The washed and dried boron phosphate hollow spheres are placed in a tubular furnace, the temperature is controlled by program under the atmosphere of ammonia gas, and the heating rate is 5oC/min, annealing at a certain temperature for a period of time, 900oC, annealing and naturally cooling to obtain the boron nitride/boron phosphate sandwich hollow sphere.
In the step (1), the molar ratio of the boron oxide to the diammonium phosphate is 1: 1.
annealing at 800 deg.C in air atmosphere in step (2)oAnd C, annealing for 2 h.
In the step (3), annealing is carried out at high temperature in an ammonia atmosphere, wherein the annealing temperature is 900 DEG CoC, the annealing time is 0.5-5 h.
The boron nitride/boron phosphate sandwich type hollow sphere prepared by the method.
The boron nitride/boron phosphate sandwich hollow sphere takes the boron phosphate hollow sphere as a main structure, and boron nitride exists on the inner surface and the outer surface of the boron phosphate hollow sphere, so that the compound is in a sandwich hollow sphere structure; the thickness of the boron nitride is adjustable; the boron phosphate is hollow spheres formed by particles, and the boron nitride is in a nano-layered structure; the diameter of the sandwich type hollow sphere is 1-3 microns.
The invention has the beneficial effects that:
(1) A method for preparing boron nitride/boron phosphate sandwich type hollow sphere composite material is developed.
(2) The preparation method is simple and convenient and has strong repeatability.
(3) The thickness of the boron nitride coating can be regulated.
(4) Has reference significance for other sandwich type hollow sphere composite materials.
Drawings
FIG. 1 is an X-ray powder diffraction (XRD) pattern of hollow boron phosphate spheres and boron nitride/phosphate sandwich hollow spheres prepared in example 1. BPO4: boron phosphate hollow spheres; BN @ BPO4@ BN: boron nitride/boron phosphate sandwich hollow spheres.
FIG. 2 is a Fourier Transform Infrared (FTIR) plot of boron phosphate hollow spheres and boron nitride/phosphate sandwich hollow spheres prepared in example 1. BPO4: boron phosphate hollow spheres; BN @ BPO4@ BN: boron nitride/boron phosphate sandwich hollow spheres.
FIG. 3 is an X-ray photoelectron spectroscopy (XPS) plot of boron phosphate hollow spheres and boron nitride/phosphate sandwich hollow spheres prepared in example 1. a: boron phosphate hollow spheres; b: boron nitride/boron phosphate sandwich hollow spheres.
FIG. 4 is a Scanning Electron Microscope (SEM) image of boron phosphate hollow spheres and boron nitride/phosphate sandwich hollow spheres prepared in example 1.
a: boron phosphate hollow spheres; b: boron nitride/boron phosphate sandwich hollow spheres.
FIG. 5 is a Transmission Electron Microscope (TEM) image of boron phosphate hollow spheres and boron nitride/phosphate sandwich hollow spheres prepared in example 1. a-b: TEM images of boron phosphate hollow spheres prepared in example 1; c-e: TEM image of boron nitride/phosphate sandwich hollow spheres; (ii) a f: e picture corresponding to position high resolution TEM picture; (ii) a g-h: high-resolution TEM image of the edge of the sandwich hollow sphere; i: j image corresponding position high resolution TEM image; j; TEM image of boron nitride/phosphate sandwich hollow sphere; k: the corresponding position of the j diagram is enlarged; i: the k-map corresponds to a positional high resolution TEM image.
FIG. 6 is a Scanning Electron Microscope (SEM) image of boron phosphate hollow spheres and boron nitride/phosphate sandwich hollow spheres prepared with different annealing times in ammonia gas atmosphere. a is 0.5 h; b is 1 h; c is 3 h; d is 5 h.
Detailed Description
In order to make the present invention more comprehensible, the technical solutions of the present invention are further described below with reference to specific embodiments, but the present invention is not limited thereto.
The preparation method comprises the following steps:
Boron oxide (1.39 g) and diammonium phosphate (2.64 g) were mixed and ground uniformly. And pouring the uniformly ground powder into an alumina crucible, and placing the alumina crucible into a tubular furnace. Under a static air atmosphere, with 5oC/min heating to 800oAnd C, preserving heat for 2h, naturally cooling to obtain a white hardened sample, grinding to obtain white powder, washing with water, and drying to obtain the boron phosphate hollow sphere. The washed and dried boron phosphate hollow spheres are placed in a tubular furnace, the temperature is controlled by program under the atmosphere of ammonia gas, and the heating rate is 5oC/min at 900oC, annealing for 0.5-5h, and naturally cooling to obtain the boron nitride/boron phosphate sandwich hollow sphere. The thickness of the boron nitride coating can be controlled according to the annealing time, and the longer the time is, the thicker the time is, the shorter the time is, the thinner the time is.
Example 1
Boron oxide (1.39 g) and diammonium phosphate (2.64 g) were mixed and ground uniformly. The uniformly ground powder was introduced into an alumina crucible and placed in a tube furnace. Under a static air atmosphere, with 5oC/min heating to 800oC, preserving heat for 2 hours, and then naturally cooling to obtain a white hardened sample; and grinding the white hardened sample into white powder, washing with water, and drying to obtain the boron phosphate hollow sphere. The washed and dried boron phosphate hollow spheres are placed in a tubular furnace, the temperature is controlled by program under the atmosphere of ammonia gas, and the heating rate is 5oC/min at 900oC, annealing for 0.5h, and naturally cooling to obtain the boron nitride/boron phosphate sandwich hollow sphere. (the crystal structure is shown in figures 1 and 2, the contained elements are shown in figure 3, the scanning electron microscope image is shown in figure 4, and the transmission electron microscope image is shown in figure 5).
The boron phosphate and boron nitride/boron phosphate hollow sphere composite material powder prepared by the invention is characterized by XRD (figure 1) and is positioned at 24.5o、26.8o、29.1oand 40.0oRespectively represents BPO4Characteristic diffraction of (101), (002), (110) and (112) planes. The boron nitride peak was not observed due to its low content and high dispersion. While in the infrared regionCharacteristic absorption peaks of boron phosphate and boron nitride were clearly observed, indicating the successful preparation of boron nitride and boron phosphate complexes (figure 2). Looking closely at fig. 3a, b, it is found that the sample before annealing contains only some residual nitrogen elements, whereas the sample after annealing contains a large amount of nitrogen elements, indicating the formation of boron nitride and being present on the surface of the sample. Further, as can be seen from fig. 4, the samples before and after annealing are spherical and have a diameter of 1-3 μm, but the SEM pictures of the samples after annealing show many bright stripes, which are mainly caused by the poor conductivity of boron nitride, which covers the surface of boron phosphate. A more pronounced hollow structure was observed in the TEM image, further confirming the structure of the hollow spheres. In FIG. 5, a and b are TEM images of boron phosphate, and c-I are TEM images of boron nitride/boron phosphate. The observation and comparison show that the boron nitride indeed covers the inner and outer surfaces of the boron phosphate ball to form a hollow ball structure similar to a sandwich.
Example 2
The washed and dried boron phosphate hollow spheres are placed in a tubular furnace, the temperature is controlled by program under the atmosphere of ammonia gas, and the heating rate is 5oC/min at 900oC annealing for 1h, and the rest steps are the same as example 1.
Example 3
The washed and dried boron phosphate hollow spheres are placed in a tubular furnace, the temperature is controlled by program under the atmosphere of ammonia gas, and the heating rate is 5oC/min at 900oC annealing for 3h, and the rest steps are the same as example 1.
Example 4
the washed and dried boron phosphate hollow spheres are placed in a tubular furnace, the temperature is controlled by program under the atmosphere of ammonia gas, and the heating rate is 5oC/min at 900oC annealing for 5h, and the rest steps are the same as example 1.
Examples 1-4 BN @ BPO prepared at different anneal times4The SEM image of @ BN is shown in FIG. 6, it is evident that the thickness of the BN layer increases with increasing annealing time.
The above description is only a preferred embodiment of the present invention, and all equivalent changes and modifications made in accordance with the claims of the present invention should be covered by the present invention.
Claims (7)
1. a preparation method of a boron nitride/boron phosphate sandwich type hollow sphere is characterized by comprising the following steps: the boron nitride/boron phosphate sandwich hollow sphere is formed by taking boron oxide, diammonium hydrogen phosphate and ammonia gas as raw materials, firstly reacting the boron oxide and the diammonium hydrogen phosphate in one step to generate the boron phosphate hollow sphere, and then growing a layer of boron nitride on the inner surface and the outer surface of the boron phosphate hollow sphere respectively.
2. The method for preparing the boron nitride/boron phosphate sandwich hollow sphere according to claim 1, which comprises the following steps:
(1) uniformly grinding boron oxide and diammonium hydrogen phosphate according to a certain proportion, and transferring the mixture into a crucible;
(2) The crucible is placed in a tube furnace, the temperature is controlled by program, and the heating rate is 5oC/min, annealing at a certain temperature for a period of time, naturally cooling, washing with water, and drying to obtain boron phosphate hollow spheres;
(3) The washed and dried boron phosphate hollow spheres are placed in a tubular furnace, the temperature is controlled by program under the atmosphere of ammonia gas, and the heating rate is 5oC/min, annealing at a certain temperature for a period of time, and naturally cooling to obtain the boron nitride/boron phosphate sandwich hollow sphere.
3. The method for preparing the boron nitride/boron phosphate sandwich hollow sphere according to claim 1, wherein the method comprises the following steps: in the step (1), the molar ratio of the boron oxide to the diammonium phosphate is 1: 1.
4. The method for preparing the boron nitride/boron phosphate sandwich hollow sphere according to claim 1, wherein the method comprises the following steps: in the step (2), high-temperature annealing is carried out in the air atmosphere, and the annealing temperature is 800oAnd C, annealing for 2 h.
5. The method for preparing the boron nitride/boron phosphate sandwich hollow sphere according to claim 1, wherein the method comprises the following steps: step (a)3) in the high temperature annealing in the ammonia atmosphere, the annealing temperature is 900 DEGoC, the annealing time is 0.5-5 h.
6. A boron nitride/phosphate sandwich hollow sphere made according to the method of claims 1-5.
7. The boron nitride/boron phosphate sandwich hollow sphere of claim 6, wherein: the boron nitride/boron phosphate sandwich hollow sphere takes the boron phosphate hollow sphere as a main structure, and boron nitride exists on the inner surface and the outer surface of the boron phosphate hollow sphere, so that the compound is in a sandwich hollow sphere structure; the thickness of the boron nitride is adjustable; the boron phosphate is hollow spheres formed by particles, and the boron nitride is in a nano-layered structure; the diameter of the sandwich type hollow sphere is 1-3 microns.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114436225A (en) * | 2022-03-02 | 2022-05-06 | 福州大学 | Boron nitride-based bowl-shaped foam material and preparation method thereof |
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| DE3826453A1 (en) * | 1988-08-04 | 1990-02-08 | Bitzer Diethelm | Clays |
| CN101045828A (en) * | 2006-07-03 | 2007-10-03 | 张义纲 | Phosphate film-coated powder and preparation method thereof |
| CN103043633A (en) * | 2013-01-09 | 2013-04-17 | 广西大学 | Method for preparing hexagonal boron nitride nano composite structure |
| CN107265415A (en) * | 2017-05-24 | 2017-10-20 | 河海大学 | A kind of method that urea auxiliary hot soarfing prepares mesoporous boron nitride from boron nitride |
| CN107876076A (en) * | 2017-11-01 | 2018-04-06 | 大连理工大学 | A kind of non-metallic catalyst, its optimization method and application for methane selectively oxidizing |
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Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| USH736H (en) * | 1987-02-27 | 1990-02-06 | The United Stated Of America As Represented By The Department Of Energy | Process for making boron nitride using sodium cyanide and boron |
| DE3826453A1 (en) * | 1988-08-04 | 1990-02-08 | Bitzer Diethelm | Clays |
| CN101045828A (en) * | 2006-07-03 | 2007-10-03 | 张义纲 | Phosphate film-coated powder and preparation method thereof |
| CN103043633A (en) * | 2013-01-09 | 2013-04-17 | 广西大学 | Method for preparing hexagonal boron nitride nano composite structure |
| CN107265415A (en) * | 2017-05-24 | 2017-10-20 | 河海大学 | A kind of method that urea auxiliary hot soarfing prepares mesoporous boron nitride from boron nitride |
| CN107876076A (en) * | 2017-11-01 | 2018-04-06 | 大连理工大学 | A kind of non-metallic catalyst, its optimization method and application for methane selectively oxidizing |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114436225A (en) * | 2022-03-02 | 2022-05-06 | 福州大学 | Boron nitride-based bowl-shaped foam material and preparation method thereof |
| CN114436225B (en) * | 2022-03-02 | 2023-02-28 | 福州大学 | Boron nitride-based bowl-shaped foam material and preparation method thereof |
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