阅读说明：本技术 一种晶态红磷的液相制备方法 (Liquid phase preparation method of crystalline red phosphorus ) 是由 严清峰 孙召建 于 2021-08-20 设计创作，主要内容包括：本发明属于功能材料技术领域,具体而言,涉及一种晶态红磷的液相制备方法。该方法包括：将非晶红磷与胺类溶剂按照一定比例混合并置于反应釜内,密封反应釜；随后将反应釜置于烘箱升温到150～300℃,并保温反应20～40小时,使非晶红磷转化为晶态红磷；自然冷却至室温,采用能溶解胺类溶剂的试剂清洗产物,真空干燥产物后即得到晶态红磷。本发明方法,因为在液相环境下实现晶态红磷制备,因此避免了中间产品白磷,既保证安全,又有利于环境保护,其中的低温反应满足节能环保的特点,因此本发明方法能够以较低的成本和较高的安全环保特性制得晶态红磷,而且可以较高的收率制得晶态红磷,得到的晶态红磷有望应用于光催化和储能领域。(The invention belongs to the technical field of functional materials, and particularly relates to a liquid-phase preparation method of crystalline red phosphorus. The method comprises the following steps: mixing amorphous red phosphorus and an amine solvent according to a certain proportion, placing the mixture into a reaction kettle, and sealing the reaction kettle; then placing the reaction kettle in an oven, heating to 150-300 ℃, and carrying out heat preservation reaction for 20-40 hours to convert the amorphous red phosphorus into crystalline red phosphorus; naturally cooling to room temperature, cleaning the product by adopting a reagent capable of dissolving an amine solvent, and drying the product in vacuum to obtain the crystalline red phosphorus. According to the method, the crystalline red phosphorus is prepared in a liquid phase environment, so that an intermediate product of white phosphorus is avoided, safety is guaranteed, environmental protection is facilitated, and low-temperature reaction meets the characteristics of energy conservation and environmental protection.)

1. A liquid phase preparation method of crystalline red phosphorus is characterized by comprising the following steps:

(1) mixing amorphous red phosphorus with an amine solvent to obtain a mixed solution;

(2) heating the mixed solution, and carrying out heat preservation reaction to convert the amorphous red phosphorus into crystalline red phosphorus;

(3) and filtering the crystalline red phosphorus, cleaning the product by adopting a reagent capable of dissolving an amine solvent, and drying the cleaned product in vacuum to obtain the crystalline red phosphorus.

2. The liquid-phase preparation method of crystalline red phosphorus according to claim 1, wherein in the step (1), the mass ratio of the amorphous red phosphorus to the amine-based solvent is (20-50): 1.

3. The liquid-phase preparation method of crystalline red phosphorus according to claim 1, wherein the amine solvent in step (1) is one or more selected from oleylamine, ethylenediamine, diethylenetriamine, n-butylamine, 1, 2-propylenediamine, and ethanolamine.

4. The liquid-phase preparation method of crystalline red phosphorus according to claim 1, wherein in the step (2), the temperature of the mixed solution is raised to 150-300 ℃ within 3 hours, and the reaction is carried out for 20-40 hours under the condition of heat preservation.

5. The liquid-phase preparation method of crystalline red phosphorus according to claim 1, wherein in the step (3), the reagent capable of dissolving the amine solvent is acetone, isopropanol, deionized water or absolute ethyl alcohol.

6. The method according to claim 1, wherein in step (3), the product is dried under vacuum under the following conditions: drying for 2-10 hours at 30-80 ℃ under the vacuum degree of 10-50 Pa.

7. Crystalline red phosphorus, characterized in that it is obtained by a process according to any one of claims 1 to 6.

Technical Field

The invention belongs to the technical field of functional materials, and particularly relates to a liquid-phase preparation method of crystalline red phosphorus.

Background

Elemental phosphorus exists primarily as three allotropes, including white phosphorus, black phosphorus, and red phosphorus. White phosphorus is chemically active and readily pyrophoric at 40 ℃. White phosphorus can be used for preparing smoke bombs and combustion bombs in military affairs, and can also be used as a precursor to synthesize phosphorus-containing pesticides, fertilizers and the like. Black phosphorus is a two-dimensional semiconductor material with a layered honeycomb-like corrugated structure, the band gap of which can be controlled by the number of layers. In addition, the black phosphorus has excellent carrier mobility and photoelectric characteristics, and is widely applied to photoelectric devices, catalysis and energy storage fields.

Red phosphorus is the most common allotrope of phosphorus in daily life. On one hand, red phosphorus is widely applied to the preparation and synthesis of matches, pesticides and flame retardants; in addition, red phosphorus can also be used as a raw material for preparing a phosphorus-based semiconductor compound and used as a semiconductor material dopant. Due to its excellent band structure and high theoretical specific capacity (2596mAh g)^-1) The red phosphorus has good application prospect in the fields of photocatalysis, lithium ion batteries, sodium ion batteries and the like. At present, the preparation of crystalline red phosphorus mainly adopts a high-temperature chemical vapor transport method. Firstly, sealing a precursor amorphous red phosphorus and a transport agent in a quartz tube in vacuum, then driving the amorphous red phosphorus to be converted into gaseous white phosphorus at high temperature (550-650 ℃), and finally, re-nucleating and crystallizing the white phosphorus at a cooling stage to grow to prepare the crystalline red phosphorus. Michael rock et al 2005 uses amorphous red phosphorus as precursor, I₂The simple substance is used as a transport agent, and the crystalline red phosphorus is successfully prepared at 590 ℃ (Angew. chem. int. Ed.2005,44, 7616-. In 2013 Tom Nilges et al will transport agent I₂Replacement with CuCl₂Crystalline red phosphorus (Z.Anorg.Allg.chem.2013,639,2741-2743) is obtained at high temperatures of 550 ℃. In 2020, CN111646441A discloses a method for preparing a red phosphor powder by using amorphous red phosphorus and I₂A high-temperature preparation method of crystalline red phosphorus with a simple substance as a raw material. However, the above-mentioned high-temperature chemical vapor transport methods have several disadvantages.

Disclosure of Invention

The present invention is intended to solve the problems of the prior art to at least some extent, and based on the discovery and recognition by the present inventors of the following facts and problems, the existing methods for preparing crystalline red phosphorus by high temperature chemical vapor transport have disadvantages: (1) the highly toxic and flammable chemicals, namely white phosphorus, serving as a reaction intermediate are likely to remain in the quartz tube, so that potential safety hazards exist; (2) the quartz tube needs vacuum flame sealing, the required equipment is complex, and the large-scale and industrial production is not facilitated; (3) the preparation process needs high temperature (550 ℃ and 650 ℃), and a large amount of energy is consumed.

The invention aims to provide a liquid phase preparation method of crystalline red phosphorus, which improves the existing preparation method of the crystalline red phosphorus to reduce the preparation cost of the crystalline red phosphorus and ensure that the preparation of the crystalline red phosphorus is safer and more environment-friendly, thereby facilitating the industrialization and scale preparation of the crystalline red phosphorus.

The embodiment of the invention provides a liquid-phase preparation method of crystalline red phosphorus, which comprises the following steps:

(1) mixing amorphous red phosphorus with an amine solvent to obtain a mixed solution;

(2) heating the mixed solution, and carrying out heat preservation reaction to convert the amorphous red phosphorus into crystalline red phosphorus;

(3) and filtering the crystalline red phosphorus, cleaning the product by adopting a reagent capable of dissolving an amine solvent, and drying the cleaned product in vacuum to obtain the crystalline red phosphorus.

In some embodiments, in the step (1), the mass ratio of the amorphous red phosphorus to the amine solvent is (20-50): 1.

In some embodiments, the amine solvent in step (1) is one or more selected from oleylamine, ethylenediamine, diethylenetriamine, n-butylamine, 1, 2-propanediamine, and ethanolamine, and is mixed in any proportion.

In some embodiments, in the step (2), the temperature of the mixed solution is raised to 150-300 ℃ within 3 hours, and the reaction is performed for 20-40 hours under the condition of heat preservation.

In some embodiments, in the step (3), the reagent capable of dissolving the amine solvent is acetone, isopropanol, deionized water or absolute ethyl alcohol.

In some embodiments, in step (3), the product vacuum drying conditions are: drying for 2-10 hours at 30-80 ℃ under the vacuum degree of 10-50 Pa.

In the embodiment of the invention, the provided crystalline red phosphorus is prepared by adopting the method.

The liquid phase preparation method of the crystalline red phosphorus provided by the invention has the advantages that:

1. the liquid phase preparation method of the crystalline red phosphorus realizes the preparation of the crystalline red phosphorus in a liquid phase environment, thereby avoiding the intermediate product white phosphorus, ensuring the safety and being beneficial to environmental protection.

2. The liquid phase preparation method of the crystalline red phosphorus has simple preparation process, and large-scale industrial production can be realized by using a large-volume or more hydrothermal kettles.

3. According to the liquid phase preparation method of the crystalline red phosphorus, the low-temperature reaction meets the characteristics of energy conservation and environmental protection, so that the method can be used for preparing the crystalline red phosphorus with lower cost and higher safety and environmental protection characteristics, and can be used for preparing the crystalline red phosphorus with higher yield, and the obtained crystalline red phosphorus is expected to be applied to the fields of photocatalysis and energy storage.

Additional aspects and advantages of the invention will be set forth in part in the description which follows and, in part, will be obvious from the description, or may be learned by practice of the invention.

Drawings

In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings needed to be used in the embodiments will be briefly described below. It is obvious that the drawings in the following description are only some embodiments of the invention, and that for a person skilled in the art, other drawings can be derived from them without inventive effort. The accompanying drawings, which are included to provide a further understanding of the invention and are incorporated in and constitute a part of this specification, illustrate embodiments of the invention and together with the description serve to explain the principles of the invention and not to limit the invention. In the drawings:

FIG. 1 is a photographic image of crystalline red phosphorus obtained in example 1 of the process of the present invention.

FIG. 2 is an X-ray diffraction pattern (XRD) of the starting amorphous red phosphorus of the present invention and the crystalline red phosphorus obtained in example 1.

FIG. 3 is a Scanning Electron Micrograph (SEM) of crystalline red phosphorus prepared in example 1.

Fig. 4 is a Raman plot (Raman) of crystalline red phosphorus prepared in example 1.

FIG. 5 is a High Resolution Transmission Electron Micrograph (HRTEM) of crystalline red phosphorus prepared in example 1.

FIG. 6 is an X-ray diffraction pattern (XRD) of crystalline red phosphorus prepared in example 2.

FIG. 7 is an X-ray diffraction pattern (XRD) of crystalline red phosphorus prepared in example 3.

FIG. 8 is an X-ray diffraction pattern (XRD) of crystalline red phosphorus prepared in example 4.

FIG. 9 is an X-ray diffraction pattern (XRD) of crystalline red phosphorus prepared in example 5.

FIG. 10 is an X-ray diffraction pattern (XRD) of crystalline red phosphorus prepared in example 6.

FIG. 11 is an X-ray diffraction pattern (XRD) of crystalline red phosphorus prepared in example 7.

Detailed Description

The following describes in detail specific embodiments of the present invention. It should be understood that the detailed description and specific examples, while indicating the present invention, are given by way of illustration and explanation only, not limitation.

The liquid phase preparation method of the crystalline red phosphorus provided by the invention comprises the following steps:

(1) mixing amorphous red phosphorus with an amine solvent to obtain a mixed solution;

(2) heating the mixed solution, and carrying out heat preservation reaction to convert the amorphous red phosphorus into crystalline red phosphorus;

(3) and filtering the crystalline red phosphorus, cleaning the product by adopting a reagent capable of dissolving an amine solvent, and drying the cleaned product in vacuum to obtain the crystalline red phosphorus.

According to the liquid phase preparation method of the crystalline red phosphorus, the mass ratio of the amorphous red phosphorus to the amine solvent in the step (1) is (20-50): 1.

According to the liquid phase preparation method of the crystalline red phosphorus, the amine solvent in the step (1) is one or more of oleylamine, ethylenediamine, diethylenetriamine, n-butylamine, 1, 2-propanediamine and ethanolamine which are mixed in any proportion.

According to the liquid phase preparation method of the crystalline red phosphorus, in the step (2), the temperature of the mixed solution is raised to 150-300 ℃ within 3 hours, and the heat preservation reaction is carried out for 20-40 hours.

According to the liquid phase preparation method of crystalline red phosphorus, in the step (3), the reagent capable of dissolving the amine solvent is acetone, isopropanol, deionized water or absolute ethyl alcohol.

The liquid phase preparation method of the crystalline red phosphorus, provided by the invention, comprises the following steps of (3): drying for 2-10 hours at 30-80 ℃ under the vacuum degree of 10-50 Pa.

In the liquid phase method for producing crystalline red phosphorus of the present invention, the shape of the amorphous red phosphorus to be used is not particularly limited, and powdery, flaky, or massive red phosphorus can be used, and in the present invention, powdery red phosphorus is preferably used, and the particle diameter thereof is preferably 0.1 to 2 mm.

The present invention will be described in detail below by way of examples.

Example 1

3.5g of amorphous red phosphorus powder (with the purity of 98.9 percent and the particle diameter of 0.1-2mm) and 70mL of ethanolamine are uniformly mixed, then the mixture is placed in a reaction kettle with the volume of 100mL, and the reaction kettle is sealed. Then placing the reaction kettle in an oven for 3 hours, heating to 300 ℃, and carrying out heat preservation reaction for 40 hours to convert the amorphous red phosphorus into crystalline red phosphorus; then naturally cooling to room temperature. Vacuum filtering, washing the product with absolute ethyl alcohol, and vacuum drying at 50 deg.C and 10Pa for 10 hr to obtain crystalline red phosphorus.

Wherein FIG. 1 is a photographic image of the crystalline red phosphorus produced, which is a red product. Fig. 2 is an X-ray diffraction (XRD) pattern of the starting amorphous red phosphorus and the crystalline red phosphorus prepared in example 1, and the XRD pattern of the starting amorphous red phosphorus shows only significant swelling and exhibits its amorphous characteristics. The obvious diffraction peak in the XRD spectrum of the crystalline red phosphorus of the product shows that the product has excellent crystallinity. FIG. 3 is a Scanning Electron Microscope (SEM) image of crystalline red phosphorus prepared in example 1. FIG. 4 is a Raman (Raman) plot of crystalline red phosphorus prepared in example 1. Fig. 5 is a High Resolution Transmission Electron Microscopy (HRTEM) image of crystalline red phosphorus prepared in example 1, with clear lattice fringes indicating excellent crystallinity of the crystalline red phosphorus.

Example 2

3g of amorphous red phosphorus powder (with the purity of 98.9 percent and the particle size of 0.1-2mm) and 70mL of oleylamine are mixed uniformly, then the mixture is placed in a reaction kettle with the volume of 100mL, and the reaction kettle is sealed. Then placing the reaction kettle in an oven for 3 hours, heating to 270 ℃, and carrying out heat preservation reaction for 38 hours to convert the amorphous red phosphorus into crystalline red phosphorus; then naturally cooling to room temperature. Vacuum filtering, cleaning the product with acetone, and vacuum drying at 60 deg.C and 10Pa for 6 hr to obtain crystalline red phosphorus.

Wherein, fig. 6 is the X-ray diffraction (XRD) pattern of the crystalline red phosphorus prepared in example 2, and the diffraction peak is obvious in the XRD pattern of the crystalline red phosphorus of the product, which shows the excellent crystallinity.

Example 3

2.5g of amorphous red phosphorus powder (with the purity of 98.9 percent and the particle diameter of 0.1-2mm) and 70mL of diethylenetriamine are mixed uniformly, then the mixture is placed in a reaction kettle with the volume of 100mL, and the reaction kettle is sealed. Then placing the reaction kettle in an oven for 3 hours, heating to 250 ℃, and carrying out heat preservation reaction for 35 hours to convert the amorphous red phosphorus into crystalline red phosphorus; then naturally cooling to room temperature. Vacuum filtering, washing the product with isopropanol, and vacuum drying at 40 deg.C and 30Pa for 8 hr to obtain crystalline red phosphorus.

Wherein, fig. 7 is the X-ray diffraction (XRD) pattern of the crystalline red phosphorus prepared in example 3, and the diffraction peak is obvious in the XRD pattern of the crystalline red phosphorus of the product, which shows the excellent crystallinity.

Example 4

2.0g of amorphous red phosphorus powder (with the purity of 98.9 percent and the particle size of 0.1-2mm) and 70mL of 1, 2-propane diamine are mixed uniformly, then the mixture is placed in a reaction kettle with the volume of 100mL, and the reaction kettle is sealed. Then placing the reaction kettle in an oven for 3 hours, heating to 220 ℃, and carrying out heat preservation reaction for 32 hours to convert the amorphous red phosphorus into crystalline red phosphorus; then naturally cooling to room temperature. Vacuum filtering, cleaning the product with acetone, and vacuum drying at 50 deg.C and 50Pa for 6 hr to obtain crystalline red phosphorus.

Wherein, fig. 8 is the X-ray diffraction (XRD) pattern of the crystalline red phosphorus prepared in example 4, and the diffraction peak is obvious in the XRD pattern of the crystalline red phosphorus of the product, which shows the excellent crystallinity.

Example 5

1.5g of amorphous red phosphorus powder (with the purity of 98.9 percent and the particle diameter of 0.1-2mm) and 70mL of n-butylamine are uniformly mixed, then the mixture is placed in a reaction kettle with the volume of 100mL, and the reaction kettle is sealed. Then placing the reaction kettle in an oven for 3 hours, heating to 200 ℃, and carrying out heat preservation reaction for 30 hours to convert the amorphous red phosphorus into crystalline red phosphorus; then naturally cooling to room temperature. Vacuum filtering, washing the product with deionized water, and vacuum drying at 70 deg.C and 20Pa for 5 hr to obtain crystalline red phosphorus.

Wherein, FIG. 9 is the X-ray diffraction (XRD) pattern of the crystalline red phosphorus prepared in example 5, the XRD pattern of the crystalline red phosphorus product has obvious diffraction peaks and slightly low crystallinity.

Example 6

3.0g of amorphous red phosphorus powder (with the purity of 98.9 percent and the particle diameter of 0.1-2mm) and 70mL of mixed solvent of 1, 2-propane diamine and ethanolamine are mixed uniformly, then the mixture is placed in a reaction kettle with the volume of 100mL, and the reaction kettle is sealed. Then placing the reaction kettle in an oven for 3 hours, heating to 180 ℃, and carrying out heat preservation reaction for 25 hours to convert the amorphous red phosphorus into crystalline red phosphorus; then naturally cooling to room temperature. Vacuum filtering, cleaning the product with ethanol, and vacuum drying at 40 deg.C and 60Pa for 6 hr to obtain crystalline red phosphorus.

Wherein, FIG. 10 is the X-ray diffraction (XRD) pattern of the crystalline red phosphorus prepared in example 6, the XRD pattern of the crystalline red phosphorus product has obvious diffraction peaks and slightly low crystallinity.

Example 7

3.0g of amorphous red phosphorus powder (with the purity of 98.9 percent and the particle diameter of 0.1-2mm) and 70mL of mixed solvent of oleylamine and n-butylamine are mixed uniformly, then the mixture is placed in a reaction kettle with the volume of 100mL, and the reaction kettle is sealed. Then placing the reaction kettle in an oven for 3 hours, heating to 150 ℃, and carrying out heat preservation reaction for 20 hours to convert the amorphous red phosphorus into crystalline red phosphorus; then naturally cooling to room temperature. Vacuum filtering, washing the product with deionized water, and vacuum drying at 80 deg.C and 50Pa for 4 hr to obtain crystalline red phosphorus.

Wherein, FIG. 11 is the X-ray diffraction (XRD) pattern of the crystalline red phosphorus prepared in example 7, the XRD pattern of the crystalline red phosphorus product has obvious diffraction peaks and poor crystallinity.

The preferred embodiments of the present invention have been described in detail, however, the present invention is not limited to the specific details of the above embodiments, and various simple modifications may be made to the technical solution of the present invention within the technical idea of the present invention, and these simple modifications are within the protective scope of the present invention.

It should be noted that the various technical features described in the above embodiments can be combined in any suitable manner without contradiction, and the invention is not described in any way for the possible combinations in order to avoid unnecessary repetition.