CN110330000A - A kind of preparation method of nanometer of red phosphorus - Google Patents

Abstract

The invention belongs to technical field of material, specially a kind of nanometer of red phosphorus preparation method.The method of the present invention includes: the amine aqueous solution for preparing phosphorus；Prepare nanometer red phosphorus.Wherein, by adjusting the concentration of dilute hydrochloric acid, control the grain diameter of nanometer red phosphorus: dilute hydrochloric acid concentration is 0-1.0 mol/L, and the grain diameter of nanometer red phosphorus is 20-50 nm.Present invention process is simple, and synthesis is convenient；The impurity that reaction process generates is highly soluble in water and ethyl alcohol, it is easy to be removed；Low energy consumption, sustainable, the time is short, at low cost；Yield is high, easy scale；It may be used as the universal synthesis method of red phosphorus based composites.

Description

A kind of preparation method of nanometer red phosphorus

technical field

The invention belongs to the technical field of material preparation, and in particular relates to a preparation method of nanometer red phosphorus.

Background technique

Phosphorus has a similar structure compared to carbon, such as layered black phosphorus, phosphorene, red phosphorus, phosphorene nanotubes, and phosphorene-based fullerenes with graphite, graphene, amorphous carbon, carbon nanotubes, and fullerenes Alkenes are similar. ^[1] Therefore, phosphorus is the best substitute for carbon materials. Moreover, phosphorus is rich in content and widely exists in nature. Phosphorus has three isomers, namely white phosphorus, red phosphorus, black phosphorus and blue phosphorus. White phosphorus is highly toxic, and it is easy to spontaneously combust in the air, so it should not be used. Both red phosphorus and black phosphorus have stable chemical properties and are widely used in PETs and optoelectronic devices, electrocatalysis, thermoelectric devices, batteries, photocatalysis, flexible electronics, supercapacitors, and other applications. However, the preparation of black phosphorus mostly requires high temperature and high pressure, while red phosphorus is not only chemically stable, but also commercially available and rich in resources, so red phosphorus has been widely studied in many applications. In most applications, red phosphorus nanocrystallization is required. The methods of red phosphorus nanometerization are usually ball milling method and evaporative condensation method. These two methods are simple and can be used as a general preparation method for phosphorus-based materials. ^{[2, 3]} However, these two methods are high in energy consumption, unsustainable, and the particle size of the prepared phosphorus is not uniform. The evaporation and condensation method inevitably produces white phosphorus during the phase transition.

_{Preparation of} red _phosphorus by _wet chemical method can effectively control the particle size _of phosphorus. For example, Zhu et al ^. Red phosphorus hollow nanospheres with uniform particles; Bian et al. ^[5] prepared red phosphorus hollow porous nanospheres in CTAB as an additive through redox reaction of PI ₃ with ethylene glycol and post-boiling process. However, in the above two methods, the impurities produced by the reaction are difficult to remove, and the reagents used in the reaction are all highly flammable and explosive substances, and are highly toxic, which are not suitable for the actual production of red phosphorus-based nanomaterials.

The ideal wet chemical method for synthesizing nano-red phosphorus should be simple and completed at room temperature. The chemical reagents used in the reaction should be commercial red phosphorus or other environmentally friendly, low-cost and safe materials, and no impurities should be generated or easily removed during the synthesis of nanometer red phosphorus.

The invention creatively prepares nanometer red phosphorus, adopts commercial red phosphorus as a raw material, and is easy to remove impurities generated during the reaction process, which are easily soluble in water and ethanol at room temperature. Compared with ball milling and evaporative condensation methods, the method has low energy consumption, sustainable, short time and low cost. Compared with the above two wet chemical methods, the method has high yield and is easy to scale up. More importantly, this method can be used as a general synthetic method for red phosphorus-based composites.

references:

[1] Y. Segawa, H. Ito, K. Itami, Nat. Rev. Mater. 2016, 1 , 15002.

[2] YQ Fu, QL Wei, GX Zhang, SH Sun. Adv. Energy Mater. 2018, 1702849.

[3] WL Liu, HQ Zhi, XB Yu, Energy Storage Mater. 2019, 16, 290-322.

[4] JB Zhou, XY Liu, WL Cai, YC Zhu, JW Liang, KL Zhang, Y. Lan, ZH Jiang, GM Wang, YT Qian, Adv. Mater. 2017, 1700214.

[5] S. Liu, H. Xu, X. F. Bian, J. K. Feng, J. Liu, Y. H. Yang, C. Yuan, Y. L. An, R. H. Fan, L. J. Ci. ACS Nano 2018, 12 (7), 7380-7387.

Contents of the invention

The purpose of the present invention is to provide a nano-red phosphorus preparation method with simple process and easy scale, so as to meet the needs of actual production and scientific research.

The preparation method of nano red phosphorus provided by the invention, the principle of its reaction is:

R-CH ₂ -CH ₂ -NH ₂ +P _n →(R-CH ₂ -CH ₂ -NH ₃ ⁺ )( R-CH ₂ -CH ₂ -NH-P _n ^- ) (1)

(2).

The concrete steps of preparation are:

(1) Preparation of phosphorus amine solution: add red phosphorus to ethylenediamine, the concentration of red phosphorus in the amine solution can be 0.001 g/ml-10 g/ml, then stir at 25-150 ℃ for 2- 36 hours;

(2) Preparation of nano-red phosphorus: Measure a certain volume of amine solution of phosphorus, and then add dilute hydrochloric acid with a concentration of 0-1 mol/L to it at a rate of 0.5-1000 ml/h. The volume ratio with dilute hydrochloric acid is 1-1/50; finally, it is centrifuged and washed with deionized water, and then freeze-dried.

In the present invention, the particle size of the nano-red phosphorus is controlled by adjusting the concentration of dilute hydrochloric acid: the concentration of dilute hydrochloric acid is 0-1 mol/L, and the particle size of the nano-red phosphorus is 20-50 nm.

In the present invention, the solvent may be amine solvents such as ethylenediamine, butylamine, triethylamine and the like.

The present invention has the following significant advantages:

(1) Using commercial red phosphorus as raw material;

(2) At room temperature, the process is simple and the synthesis is convenient;

(3) The impurities produced during the reaction process are easily soluble in water and ethanol, and can be easily removed;

(4) Compared with the ball milling and evaporation methods, the energy consumption of this method is reduced by 70%-90%, sustainable, the time is shortened from tens of hours to 1-60 minutes, and the cost is low;

(5) Compared with the other two wet chemical methods, the yield of this method is increased to 80-100%, and it is easy to scale;

(6) It can be used as a general synthetic method for red phosphorus-based composites.

Description of drawings

Fig. 1 is the SEM image of the sample obtained in Example 1.

Fig. 2 is the XRD spectrogram of the sample obtained in Example 1.

Fig. 3 is the SEM image of the sample obtained in Example 2.

Detailed ways

Embodiment 1. Particle diameter is the preparation of 50 nm nanometer red phosphorus

Add red phosphorus into the ethylenediamine solution, the concentration of red phosphorus in the ethylenediamine solution is 10 g/ml, and then stir at 25 °C for 36 h. Then measure a certain volume of phosphorus ethylenediamine solution, and then add dropwise dilute hydrochloric acid with a concentration of 0.1 mol/L, and the volume ratio of phosphorus ethylenediamine solution to dilute hydrochloric acid is 1 at a rate of 1000 ml/h. Finally, it was centrifuged and washed with deionized water, and then freeze-dried. Compared with the ball milling and evaporation methods, the energy consumption of this method is reduced by 90%, sustainable, the time is shortened from tens of hours to 1 minute, and the cost is low; compared with the other two wet chemical methods, the yield of this method is increased to 100%. scale.

Embodiment 2. Particle diameter is the preparation of 20 nm nanometer red phosphorus

Add red phosphorus to the butylamine solution, the concentration of red phosphorus in the butylamine solution is 0.1g/ml, and then stir at 100 °C for 36 h. Then measure a certain volume of phosphorus butylamine solution, and then add dropwise dilute hydrochloric acid with a concentration of 0 mol/L to it at a rate of 100 ml/h. The volume ratio of phosphorus butylamine solution to dilute hydrochloric acid is 1/25. Finally, it was centrifuged and washed with deionized water, and then freeze-dried. Compared with the ball milling and evaporation methods, the energy consumption of this method is reduced by 80%, sustainable, the time is shortened from tens of hours to 30 minutes, and the cost is low; compared with the other two wet chemical methods, the yield of this method is increased to 90%. scale.

Embodiment 3. Particle diameter is the preparation of 35 nm nanometer red phosphorus

Add red phosphorus to the triethylamine solution, the concentration of red phosphorus in the triethylamine solution is 0.001g/ml, and then stir at 150 °C for 36 h. Then measure a certain volume of phosphorus ethylenediamine solution, and then add dropwise dilute hydrochloric acid with a concentration of 0.05 mol/L, the volume ratio of the phosphorus ethylenediamine solution to dilute hydrochloric acid at a rate of 10 ml/h is 1/50 . Finally, it was centrifuged and washed with deionized water, and then freeze-dried. Compared with the ball milling and evaporation methods, the energy consumption of this method is reduced by 70%, sustainable, the time is shortened from tens of hours to 60 minutes, and the cost is low; compared with the other two wet chemical methods, the yield of this method is increased to 90%. scale.

Claims (3)

1. a preparation method of nanometer red phosphorus, is characterized in that, concrete steps are: (1) Prepare the amine solution of phosphorus: add red phosphorus to the amine, then stir at 25-150 °C for 2-36 h; the concentration of the red phosphorus in the amine solution is 0.001g/ml-10g/ml ; (2) Preparation of nano-red phosphorus: Measure a certain volume of amine solution of phosphorus, and add dilute hydrochloric acid with a concentration of 0-1.0 mol/L dropwise at a rate of 0.5-1000 ml/h. The volume ratio of hydrochloric acid is 1~1/50; finally, it is centrifuged and washed with deionized water, and then freeze-dried. 2. The preparation method of nano red phosphorus according to claim 1, characterized in that, by adjusting the concentration of dilute hydrochloric acid, the particle size of nano red phosphorus is controlled: the concentration of dilute hydrochloric acid is 0 ~ 1.0 mol/L, and the concentration of nano red phosphorus The particle size of the particles is 20-50 nm. 3. The preparation method of nano red phosphorus according to claim 1, characterized in that ethylenediamine, butylamine or triethylamine is used as the solvent in step (1).