阅读说明：本技术 一种高活性光催化剂晶体磷材料及其制备方法 (High-activity photocatalyst crystal phosphorus material and preparation method thereof ) 是由 许并社 张帅 马淑芳 于 2021-08-25 设计创作，主要内容包括：本发明属于晶体磷材料制备技术领域,具体涉及一种高活性光催化剂晶体磷材料及其制备方法。所述方法包括以下步骤：将红磷粉末和铋粉加入到密闭环境中,升高温度到530℃以上,保温反应10-200min,反应结束后降温至室温,得到晶体磷材料。本发明以红磷和铋为原料,二者在真空环境在热处理反应,生成稳定的橙红色[P12(4)]P2[产物或者稳定的晶体紫磷材料,本发明首次实现了这两种材料的稳定制备方法,并且材料制备过程简单,高效安全,为研究晶体红磷和晶体紫磷的结构性能铺平道路,为单元素光催化剂的研究提供思路,该材料的应用前景极为广阔。(The invention belongs to the technical field of preparation of crystalline phosphorus materials, and particularly relates to a high-activity photocatalyst crystalline phosphorus material and a preparation method thereof. The method comprises the following steps: adding red phosphorus powder and bismuth powder into a closed environment, raising the temperature to over 530 ℃, carrying out heat preservation reaction for 10-200min, and cooling to room temperature after the reaction is finished to obtain the crystal phosphorus material. The invention takes red phosphorus and bismuth as raw materials, the red phosphorus and the bismuth are subjected to heat treatment reaction in a vacuum environment to generate a stable orange red [ P12(4) ] P2[ product or a stable crystal purple phosphorus material.)

1. A preparation method of a high-activity photocatalyst crystal phosphorus material is characterized by adding red phosphorus powder and bismuth powder into a closed environment, raising the temperature to over 530 ℃, carrying out heat preservation reaction for 10-200min, and cooling to room temperature after the reaction is finished to obtain the crystal phosphorus material.

2. The method for preparing a high-activity photocatalyst crystalline phosphorus material as claimed in claim 1, wherein the temperature is raised to 560-;

or raising the temperature to 530-560 ℃, carrying out heat preservation reaction, after the reaction is finished, carrying out program cooling to 280-320 ℃, continuing the heat preservation reaction, and naturally cooling to room temperature after the reaction is finished to obtain the orange red crystal red phosphorus material.

3. The high-activity photocatalyst crystalline phosphorus material of claim 2, wherein the method of adding to the closed environment is: adding red phosphorus powder and bismuth powder into a glass ampoule bottle, and vacuum sealing.

4. The highly active photocatalyst crystalline phosphor material of claim 3, wherein the reaction of red phosphorus powder and bismuth powder is carried out in a muffle furnace.

5. The high-activity photocatalyst crystalline phosphorus material as claimed in claim 4, wherein the mass ratio of red phosphorus powder to bismuth powder is 100-600: 10-60.

6. The high activity photocatalyst crystalline phosphorus material as defined in claim 5, wherein the reaction time at 530 ℃ and 560 ℃ is 10-20 min.

7. The high activity photocatalyst crystalline phosphorus material of claim 6, wherein the programmed temperature reduction rate is 0.5-2 ℃/min.

8. The method as claimed in claim 1, wherein the reaction time is 10-12h at 280-320 ℃.

9. The high-activity photocatalyst crystalline phosphorus material as claimed in claim 1, wherein the crystalline phosphorus material is sequentially washed with acetone and absolute ethanol and dried to obtain a purified phosphorus material.

10. A high activity photocatalyst crystalline phosphorus material prepared by the method of any one of claims 1 to 9.

Technical Field

The invention belongs to the technical field of phosphorus material preparation, and particularly relates to a high-activity photocatalyst crystal phosphorus material and a preparation method thereof.

Background

Single element phosphorus as two-dimensional materialThe potential properties of the material are gradually exposing the corners in a wide range of fields. Elemental phosphorus has a number of allotropes, white phosphorus and red phosphorus, in addition to the most prominent crystalline black phosphorus. The red phosphorus comprises commercial amorphous red phosphorus, and the crystalline red phosphorus material-V additionally comprises three polymeric red phosphorus materials: [ P8]P4(4)[，[P10]P2 and [ P12(4)]P2 [. (ref.: Bachhuber, F., von Apen, J., Dronskowski, R., Schmidt, P., Nilges, T., Pfitzner, A., and Weihrich, R. (2014.) The extended stability range of phosphor alloys according to Angew Chem. Engl 53, 11629. 11633; Bachhuber, F., von Apen, J., Dronskowski, R., Schmidt, P., Nilges, T., Italyzner, A., and Weihrich, R. (2015.) Van der Waals interactions in dispersions of phosphor particles, Zehryser, J. (Mat. J.: Kr. J. 35. J. sub., Pair. Schmidt, P., Zehryser, A., Pfitler, Pfihrlich., R. (2015.) The Van der interactions in which is J. (J.: Zehryser, J. E.7. catalog. J.mit einer neuartigen, the oretisch vorheresargten Form des phosphors.107, 1784-1786; pfitzner, A., and Freudenthaler, E.J.A.C.I.E. (1995 b. (CuI)3P12: A Solid contact a New Polymer of Phosphorus pretreated by theory 34, 1647-1649; pfitzner, A., and Freudenthaler, E.J.Z.F.N.B. (1997) (CuI)2P14: ein neues phosphoenolmer in einer Kupfrhalogenid-Matrix/(CuI) 2P14: a Novel Phosphorus Polymer in a Copper Halide matrix.52.) Phosphorus of each structure has specific properties, for example: black phosphorus has significant anisotropy and high carrier mobility; the fiber phosphorus with a parallel tubular structure has outstanding anisotropy and photocatalytic nitrogen fixation characteristics, and the purple phosphorus with a vertical tubular structure shows excellent performance in photocatalytic hydrogen evolution. However, due to the difficulty of obtaining materials, the structure of red phosphorus has not been well characterized, let alone exploring its properties. Therefore, there is a need to develop a method for stably preparing crystalline phosphorus materials and the use of red phosphorus materials.

Disclosure of Invention

In order to solve the technical problems, the invention provides a high-activity photocatalyst crystal phosphorus material and a preparation method thereof.

The first purpose of the invention is to provide a preparation method of a high-activity photocatalyst crystal phosphorus material, which comprises the following steps: adding red phosphorus powder and bismuth powder into a closed environment, raising the temperature to over 530 ℃, carrying out heat preservation reaction for 10-200min, and cooling to room temperature after the reaction is finished to obtain the crystal phosphorus material.

Preferably, the preparation method of the high-activity photocatalyst crystal phosphorus material is that the temperature is raised to 560-700 ℃, the heat preservation reaction is carried out for 10-200min, and the temperature is naturally reduced to room temperature after the reaction is finished, so as to obtain the deep purple phosphorus micron rod material;

or raising the temperature to 530-560 ℃, carrying out heat preservation reaction, after the reaction is finished, carrying out program cooling to 280-320 ℃, continuing the heat preservation reaction, and naturally cooling to room temperature after the reaction is finished to obtain the orange red crystal red phosphorus material.

Preferably, the method for preparing the high-activity photocatalyst crystal phosphorus material is added into a closed environment and comprises the following steps: adding red phosphorus powder and bismuth powder into a glass ampoule bottle, and vacuum sealing.

Preferably, in the preparation method of the high-activity photocatalyst crystal phosphorus material, the reaction of the red phosphorus powder and the bismuth powder is carried out in a muffle furnace.

Preferably, in the preparation method of the high-activity photocatalyst crystalline phosphorus material, the mass ratio of the red phosphorus powder to the bismuth powder is 100-600: 10-60.

Preferably, in the preparation method of the high-activity photocatalyst crystalline phosphorus material, the reaction time is 10-20min at the temperature of 530 ℃ and 560 ℃.

Preferably, in the preparation method of the high-activity photocatalyst crystal phosphorus material, the program cooling rate is 0.5-2 ℃/min.

Preferably, in the preparation method of the high-activity photocatalyst crystalline phosphorus material, the reaction time is 10-12h at the temperature of 280-320 ℃.

Preferably, in the preparation method of the high-activity photocatalyst crystal phosphorus material, the crystal phosphorus material is sequentially washed by acetone and absolute ethyl alcohol and dried to prepare the purified phosphorus material.

It is a second object of the present invention to provide a highly active photocatalyst crystalline phosphorus material prepared by the above method.

Compared with the prior art, the invention has the following beneficial effects:

1. the invention takes red phosphorus and bismuth as raw materials, the red phosphorus and the bismuth are subjected to heat treatment reaction in a vacuum environment to generate a stable orange red [ P12(4) ] P2[ product or a stable crystal purple phosphorus material, the invention realizes the stable preparation method of the two materials for the first time, and the preparation process of the materials is simple, efficient and safe, paves the way for researching the structural properties of crystal red phosphorus ([ P12(4) ] P2[) and crystal purple phosphorus, provides an idea for researching a single-element photocatalyst, and has extremely wide application prospect.

2. The high-activity photocatalyst crystal phosphorus material prepared by the invention has good application prospect in the field of photocatalysis, and researches of the invention find that the crystal red phosphorus ([ P12(4) ] P2[) and the crystal purple phosphorus material can efficiently degrade methyl orange, and the high-activity photocatalyst is a high-activity photocatalyst.

Drawings

FIG. 1 is an SEM picture of a crystalline red phosphorus material prepared in example 1;

FIG. 2 is the XRD pattern of the crystalline red phosphorus material prepared in example 1;

FIG. 3 is an SEM picture of the crystalline purple phosphorus material prepared in example 6;

FIG. 4 is an XRD pattern of the crystalline purple phosphorus material prepared in example 6;

FIG. 5 shows the results of photocatalytic degradation of methyl orange by the crystalline red phosphorus material prepared in example 1;

fig. 6 is a result of photocatalytic degradation of methyl orange of the crystalline purple phosphorus material prepared in example 6.

Detailed Description

In order that those skilled in the art will better understand the technical solutions of the present invention to be implemented, the present invention will be further described with reference to the following specific embodiments and accompanying drawings.

In the description of the present invention, reagents used are commercially available and methods used are conventional in the art, unless otherwise specified. Red phosphorus powder and bismuth powder used in the following examples are commercially available.

Example 1

A preparation method of a high-activity photocatalyst crystal phosphorus material comprises the following steps:

adding 100mg of red phosphorus powder and 20mg of bismuth powder into a glass ampoule bottle, sealing in vacuum, placing in a muffle furnace, raising the temperature to 530 ℃, carrying out heat preservation reaction for 10min, reducing the temperature to 280 ℃ at a cooling rate of 0.5/min after the reaction is finished, carrying out heat preservation reaction for 10h, and naturally cooling to room temperature after the reaction is finished to obtain the orange red crystal red phosphorus material.

FIG. 1 is an SEM picture of a crystalline red phosphorus material prepared in example 1 of the present invention, wherein the SEM picture shows that the material has a microstrip structure and has a large aspect ratio; FIG. 2 is an XRD pattern of the crystalline red phosphorus material prepared in example 1 of the present invention, showing that the sample has a higher degree of crystallinity and the diffraction peak positions correspond to those of the previously reported crystalline red phosphorus material.

Example 2

A preparation method of a high-activity photocatalyst crystal phosphorus material comprises the following steps:

adding 100mg of red phosphorus powder and 10mg of bismuth powder into a glass ampoule bottle, sealing in vacuum, placing in a muffle furnace, raising the temperature to 560 ℃, carrying out heat preservation reaction for 15min, reducing the temperature to 300 ℃ at a cooling rate of 1 ℃/min after the reaction is finished, carrying out heat preservation reaction for 11h, and naturally cooling to room temperature after the reaction is finished to obtain the orange red crystal red phosphorus material.

Example 3

A preparation method of a high-activity photocatalyst crystal phosphorus material comprises the following steps:

adding 600mg of red phosphorus powder and 10mg of bismuth powder into a glass ampoule bottle, sealing in vacuum, placing in a muffle furnace, raising the temperature to 540 ℃, carrying out heat preservation reaction for 20min, reducing the temperature to 320 ℃ at a cooling rate of 2 ℃/min after the reaction is finished, carrying out heat preservation reaction for 12h, and naturally cooling to room temperature after the reaction is finished to obtain the orange red crystal red phosphorus material.

Example 4

A preparation method of a high-activity photocatalyst crystal phosphorus material comprises the following steps:

adding 200mg of red phosphorus powder and 60mg of bismuth powder into a glass ampoule bottle, sealing in vacuum, placing in a muffle furnace, raising the temperature to 540 ℃, carrying out heat preservation reaction for 20min, reducing the temperature to 320 ℃ at a cooling rate of 2 ℃/min after the reaction is finished, carrying out heat preservation reaction for 12h, and naturally cooling to room temperature after the reaction is finished to obtain the orange red crystal red phosphorus material.

Example 5

A preparation method of a high-activity photocatalyst crystal phosphorus material comprises the following steps:

adding 300mg of red phosphorus powder and 50mg of bismuth powder into a glass ampoule bottle, sealing in vacuum, placing in a muffle furnace, raising the temperature to 540 ℃, carrying out heat preservation reaction for 20min, reducing the temperature to 320 ℃ at a cooling rate of 2 ℃/min after the reaction is finished, carrying out heat preservation reaction for 12h, and naturally cooling to room temperature after the reaction is finished to obtain the orange red crystal red phosphorus material.

Example 6

A preparation method of a high-activity photocatalyst crystal phosphorus material comprises the following steps:

adding 300mg of red phosphorus powder and 50mg of bismuth powder into a glass ampoule bottle, sealing in vacuum, placing in a muffle furnace, raising the temperature to 530 ℃, keeping the temperature for reaction for 20min, and naturally cooling to room temperature after the reaction is finished to obtain the deep purple phosphorus micron rod material.

FIG. 3 is an SEM picture of a crystalline purple phosphorus material prepared in example 6 of the present invention, wherein the SEM picture shows the material with a micron rod structure; FIG. 4 is an XRD pattern of the crystalline purple phosphorus material prepared in example 6 of the present invention, the XRD pattern shows that the sample has higher crystallinity and the diffraction peak position corresponds to the previously reported crystalline purple phosphorus material.

Example 7

A preparation method of a high-activity photocatalyst crystal phosphorus material comprises the following steps:

adding 100mg of red phosphorus powder and 60mg of bismuth powder into a glass ampoule bottle, sealing in vacuum, placing in a muffle furnace, raising the temperature to 700 ℃, keeping the temperature for reaction for 10min, and naturally cooling to room temperature after the reaction is finished to obtain the deep purple phosphorus micron rod material.

Example 8

A preparation method of a high-activity photocatalyst crystal phosphorus material comprises the following steps:

adding 100mg of red phosphorus powder and 10mg of bismuth powder into a glass ampoule bottle, sealing in vacuum, placing in a muffle furnace, raising the temperature to 600 ℃, keeping the temperature for reaction for 200min, and naturally cooling to room temperature after the reaction is finished to obtain the deep purple phosphorus micron rod material.

Comparative example 1

A preparation method of a high-activity photocatalyst crystal phosphorus material comprises the following steps:

adding 100mg of red phosphorus powder and 20mg of bismuth powder into a glass ampoule bottle, sealing in vacuum, placing in a muffle furnace, raising the temperature to 600 ℃, carrying out heat preservation reaction for 10min, reducing the temperature to 280 ℃ at a cooling rate of 0.5/min after the reaction is finished, carrying out heat preservation reaction for 10h, and naturally cooling to room temperature after the reaction is finished to obtain a black substance.

Comparative example 2

A preparation method of a high-activity photocatalyst crystal phosphorus material comprises the following steps:

adding 100mg of red phosphorus powder and 20mg of bismuth powder into a glass ampoule bottle, sealing in vacuum, placing in a muffle furnace, raising the temperature to 500 ℃, keeping the temperature for reaction for 10min, and naturally cooling to room temperature after the reaction is finished to obtain a black substance.

The following is a test of photocatalytic degradation of methyl orange as an example to demonstrate the effect of the present invention.

The specific experimental method is as follows: 10mg of the sample prepared in example 1 was weighed, added to a 100mm, 50mL solution of methyl orange, stirred, reacted by LED illumination, sampled at intervals of 10min, and subjected to absorbance test.

The experimental result is shown in fig. 5, and the degradation rate of methyl orange is as high as about 90% at about 40min, so that the high-efficiency photodegradation characteristic is shown.

In addition, 10mg of the sample prepared in example 6 was weighed, added to a 100mm, 50mL solution of methyl orange, stirred, reacted with LED light, sampled at intervals of 10min, and subjected to absorbance test.

The experimental result is shown in fig. 6, and about 80min, the degradation rate of methyl orange is about 95%, and the high-efficiency photodegradation characteristic is shown.

It should be noted that, when the present invention relates to a numerical range, it should be understood that two endpoints of each numerical range and any value between the two endpoints can be selected, and since the steps and methods adopted are the same as those in the embodiment, in order to prevent redundancy, the present invention describes a preferred embodiment. While preferred embodiments of the present invention have been described, additional variations and modifications in those embodiments may occur to those skilled in the art once they learn of the basic inventive concepts. Therefore, it is intended that the appended claims be interpreted as including preferred embodiments and all such alterations and modifications as fall within the scope of the invention.

It will be apparent to those skilled in the art that various changes and modifications may be made in the present invention without departing from the spirit and scope of the invention. Thus, if such modifications and variations of the present invention fall within the scope of the claims of the present invention and their equivalents, the present invention is also intended to include such modifications and variations.