阅读说明：本技术 一种氮化硼/磷酸硼三明治型空心球的制备方法 (Preparation method of boron nitride/boron phosphate sandwich type hollow sphere ) 是由 黄彩进 刘秋文 刘强 于 2019-10-18 设计创作，主要内容包括：本发明公开了一种氮化硼/磷酸硼三明治型空心球的制备方法,属于材料科学技术领域。本发明提出了一种氮化硼/磷酸硼三明治型空心球的制备方法,先利用了自组装和奥斯瓦尔德熟化效应,在空气中高温退火,成功得到了磷酸硼空心球结构,然后,在氨气气氛下高温退火,在磷酸硼空心球的内外表面各生长了一层氮化硼,形成了类似三明治的空心球结构。本发明方法简单,有利于大规模的工业生产,具备显著的经济和社会效益。(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.)

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 5^oC/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 5^oC/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 800^oAnd 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 DEG^oC, 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.

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 5^oC/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 5^oC/min, annealing at a certain temperature for a period of time, 900^oC, 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 C^oC, 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 5^oC/min heating to 800^oAnd 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 5^oC/min at 900^oC, 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.