阅读说明：本技术 一种化学还原法制备硒纳米颗粒的制备方法 (Preparation method for preparing selenium nanoparticles by chemical reduction method ) 是由 邹虎成 陆绍荣 庄映红 覃柳兰 李家文 梁祖珍 邓欣怡 于 2021-09-29 设计创作，主要内容包括：本发明公开了一种化学还原法制备硒纳米颗粒的制备方法,通过将1～5重量份的葡萄糖和1～5重量份的聚乙烯吡咯烷酮分别加入到10～60重量份的二乙烯三胺中充分溶解后,再加入0.2～1重量份的二氧化硒,于氩气氛围下恒温反应,反应结束后,制得硒溶液；再将制得的硒溶液置于透析袋中透析,透析过程中每间隔4-8h更换一次水,经过透析后,将透析袋内的红色液体进行冷冻干燥,经冷冻干燥后所得的固体粉末即为硒纳米颗粒。该制备方法原料易得、制备周期短、产率高、制备成本低,制得的硒纳米颗粒的粒径均匀。(The invention discloses a preparation method of selenium nanoparticles by a chemical reduction method, which comprises the steps of respectively adding 1-5 parts by weight of glucose and 1-5 parts by weight of polyvinylpyrrolidone into 10-60 parts by weight of diethylenetriamine for full dissolution, then adding 0.2-1 part by weight of selenium dioxide, carrying out constant temperature reaction in an argon atmosphere, and preparing a selenium solution after the reaction is finished; and putting the prepared selenium solution into a dialysis bag for dialysis, replacing water every 4-8h in the dialysis process, carrying out freeze drying on the red liquid in the dialysis bag after dialysis, and obtaining solid powder which is the selenium nano-particles after freeze drying. The preparation method has the advantages of easily available raw materials, short preparation period, high yield and low preparation cost, and the prepared selenium nanoparticles have uniform particle size.)

1. A method for preparing selenium nano-particles by a chemical reduction method is characterized by comprising the following steps:

1) adding 1-5 parts by weight of glucose, 1-5 parts by weight of polyvinylpyrrolidone and 0.2-1 part by weight of selenium dioxide into 10-60 parts by weight of diethylenetriamine, fully dissolving, reacting at constant temperature in an argon atmosphere, and preparing a selenium solution after the reaction is finished;

2) putting the selenium solution prepared in the step 1) into a dialysis bag for dialysis, replacing water every 4-8h in the dialysis process, after dialysis, freeze-drying the red liquid in the dialysis bag, and obtaining solid powder which is selenium nano-particles after freeze-drying.

2. The method for preparing selenium nanoparticles by chemical reduction according to claim 1, wherein the isothermal reaction in step 1) is performed for 4 hours at 150 ℃ in an argon atmosphere.

3. The method of claim 1, wherein the dialysis in step 2) is performed for 24 hours in a dialysis bag with a molecular weight cut-off of 500.

4. The method of claim 1, wherein in step 1), the glucose, polyvinylpyrrolidone and diethylenetriamine are chemically pure or more.

Technical Field

The invention belongs to the technical field of nano materials, and particularly relates to a preparation method for preparing selenium nano particles by a chemical reduction method.

Background

Nanotechnology is a technology for accurately observing, identifying and controlling the species, quantity and structural morphology of substances on a single atom and molecule level, and is a multidisciplinary crossing high-tech technology for researching the characteristics and interaction of the substances in a nanoscale range and manufacturing products with specific functions by utilizing the characteristics.

Nano-selenium is a popular material which has been developed gradually in recent years, and the preparation, characteristics and potential applications of nano-selenium are also concerned by researchers in the chemical and medical fields. The nano-selenium has the characteristics of small particle size, good dispersibility, uniform particle size and the like, so that the nano-selenium has wide application in the aspects of medicines, pesticides, cosmetics, dyes and the like.

At present, chemical vapor deposition is mainly adopted for preparing selenium nanoparticles, sodium selenate or sodium selenite is used as a raw material, and nano selenium with different particle sizes is obtained under the conditions of temperature control, vacuum, inert gas protection and the like. On the other hand, selenium resources are deficient, and the utilization rate is low, which causes great waste. Therefore, the method for preparing the selenium nano particles on a large scale by using the elemental selenium as the raw material and adopting the chemical reduction method not only can promote the practical application and the theoretical research of the selenium nano material, but also can greatly promote the development and the application of elemental selenium resources.

Disclosure of Invention

The invention aims to solve the common problems of difficulty in macroscopic preparation, complex preparation process, high cost and the like in the field of the current selenium nano materials and promote the practical application of selenium nano particles, and provides a preparation method for preparing selenium nano particles by a chemical reduction method.

The technical scheme for realizing the purpose of the invention is as follows:

a method for preparing selenium nano-particles by a chemical reduction method comprises the following steps:

1) adding 1-5 parts by weight of glucose, 1-5 parts by weight of polyvinylpyrrolidone and 0.2-1 part by weight of selenium dioxide into 10-60 parts by weight of diethylenetriamine, fully dissolving, reacting at constant temperature in an argon atmosphere, and preparing a selenium solution after the reaction is finished;

2) putting the selenium solution prepared in the step 1) into a dialysis bag for dialysis, replacing water every 4-8h in the dialysis process, after dialysis, freeze-drying the red liquid in the dialysis bag, and obtaining solid powder which is selenium nano-particles after freeze-drying.

In the step 1), the constant-temperature reaction is carried out for 4 hours in an argon atmosphere at the temperature of 150 ℃.

In the step 2), the dialysis is carried out for 24 hours in a dialysis bag with the molecular weight cutoff of 500.

In the step 1), the glucose, the polyvinylpyrrolidone and the diethylenetriamine are all chemically pure or have more than chemical purity.

The preparation method for preparing the selenium nano-particles by the chemical reduction method has the advantages of easily available raw materials, short preparation period, high yield and low preparation cost, and the prepared selenium nano-particles have uniform particle size; the prepared selenium nano-particles are tested for appearance and size by a scanning electron microscope, and the result shows that the selenium nano-particles are spherical particles with narrow particle size distribution; the particle size test is adopted for analysis, and the particle size of the prepared selenium nano particles is proved to be about 30-200 nanometers; the functional group information of the dispersed polymer is tested by Fourier infrared, and the fact that the groups of the polymer are basically unchanged before and after synthesis is confirmed. The selenium nano-particles are uniform and fine, have good water solubility, and are expected to have potential application prospects in the aspects of biological medicines, pesticides, cosmetics, dyes and the like.

Drawings

FIG. 1 is a scanning electron microscope photograph of selenium nanoparticles prepared in example 1 of the present invention;

FIG. 2 is an infrared spectrum of selenium nanoparticles prepared in example 1 of the present invention;

FIG. 3 is a graph showing the particle size distribution of selenium nanoparticles prepared in example 1 of the present invention;

FIG. 4 is a photographic view of an aqueous dispersion of selenium nanoparticles prepared in example 1 of the present invention in sunlight;

fig. 5 is a schematic view of selenium nanoparticle powder prepared in example 1 of the present invention.

Detailed Description

The invention will be further elucidated with reference to the drawings and examples, without however being limited thereto.

Example 1:

a method for preparing selenium nano-particles by a chemical reduction method comprises the following steps:

(1) respectively adding 2 parts by weight of glucose and 2 parts by weight of polyvinylpyrrolidone into a flask containing 20 parts by weight of diethylenetriamine, ultrasonically dispersing and stirring until the glucose and the polyvinylpyrrolidone are dissolved, then adding 0.5 part by weight of selenium dioxide, filling argon gas into the flask, placing the flask on an oil bath pot, heating to 150 ℃, and reacting at constant temperature for 4 hours to obtain a selenium solution;

(2) and (2) putting the selenium solution prepared in the step (1) into a dialysis bag with the molecular weight cutoff of 500 for dialysis for 24 hours, changing water at an interval of 4 hours midway, carrying out dialysis, carrying out freeze drying on red liquid in the dialysis bag, and obtaining solid powder which is selenium nano-particles after freeze drying.

And respectively carrying out a scanning electron microscope, a Fourier infrared test and a particle size test on the prepared selenium nanoparticles. The shape analysis is carried out by a scanning electron microscope, as shown in fig. 1, it can be seen from fig. 1 that the selenium nanoparticles are uniformly dispersed, have a particle size range of 50-200 nm, and are spherical. It can be seen from the infrared diagram of fig. 2 that the functional group of the polymer PVP is not changed before and after the reaction, which indicates that the selenium nanoparticles may be attached to the polymer surface by electrostatic adsorption, so that the selenium nanoparticles can be stably dispersed in the aqueous solution. The average particle size distribution of the selenium nanoparticles is analyzed through particle size analysis, and the average particle size distribution is measured to be 50-200 nm, which is consistent with the appearance observation of a scanning electron microscope shown in figure 1. Fig. 4 shows a selenium nanoparticle solution dispersed uniformly after dialysis, and freeze-drying the solution to obtain solid selenium nanoparticle powder as shown in fig. 5, which is well re-soluble in water.

Example 2:

(1) adding 1 weight part of polyvinylpyrrolidone into a flask containing 10 weight parts of diethylenetriamine, ultrasonically dispersing and stirring until the polyvinylpyrrolidone is dissolved, then respectively adding 1 weight part of selenium dioxide and 1 weight part of glucose, simultaneously stirring for 30 minutes while ultrasonically dispersing, then introducing argon protective gas into the flask, placing the flask on an oil bath pot, heating to 150 ℃, and reacting for 4 hours at constant temperature to obtain a selenium solution;

(2) and (2) putting the selenium solution obtained in the step (1) into a dialysis bag with the molecular weight cutoff of 500 for dialysis for 24 hours, changing water at an interval of 4 hours midway, carrying out dialysis, then carrying out freeze drying on the red liquid in the dialysis bag, and obtaining solid powder which is the selenium nano-particles after freeze drying.

Example 3:

(1) respectively adding 4 parts by weight of glucose and 4 parts by weight of polyvinylpyrrolidone into a flask containing 25 parts by weight of diethylenetriamine, ultrasonically dispersing and stirring until the glucose and the polyvinylpyrrolidone are dissolved, then adding 0.8 part by weight of selenium dioxide, filling argon protection gas into the flask, placing the flask on an oil bath pot, heating to 150 ℃, and reacting at constant temperature for 4 hours to obtain a selenium solution;

(2) and (2) putting the selenium solution obtained in the step (1) into a dialysis bag with the molecular weight cutoff of 500 for dialysis for 24 hours, changing water at an interval of 8 hours midway, carrying out dialysis, carrying out freeze drying on red liquid in the dialysis bag, and obtaining solid powder which is selenium nano-particles after freeze drying.

Example 4:

(1) adding 1 weight part of polyvinylpyrrolidone into a flask containing 15 weight parts of diethylenetriamine, ultrasonically dispersing and stirring until the polyvinylpyrrolidone is dissolved, then respectively adding 1 weight part of selenium dioxide and 1 weight part of glucose, simultaneously stirring for 30 minutes while ultrasonically dispersing, then introducing argon protective gas into the flask, placing the flask on an oil bath pot, heating to 150 ℃, and reacting for 4 hours at constant temperature to obtain a selenium solution;

(2) and (2) putting the selenium solution obtained in the step (1) into a dialysis bag with the molecular weight cutoff of 500 for dialysis for 24 hours, changing water at an interval of 4 hours midway, carrying out dialysis, then carrying out freeze drying on the red liquid in the dialysis bag, and obtaining solid powder which is the selenium nano-particles after freeze drying.

Example 5:

(1) respectively adding 5 parts by weight of glucose and 5 parts by weight of polyvinylpyrrolidone into a flask containing 54 parts by weight of diethylenetriamine, ultrasonically dispersing and stirring until the glucose and the polyvinylpyrrolidone are dissolved, then adding 1 part by weight of selenium dioxide, filling argon protection gas into the flask, placing the flask on an oil bath pot, heating to 150 ℃, and reacting at constant temperature for 4 hours to obtain a selenium solution;

(2) and (2) putting the selenium solution obtained in the step (1) into a dialysis bag with the molecular weight cutoff of 500 for dialysis for 24 hours, changing water at an interval of 4 hours midway, carrying out dialysis, then carrying out freeze drying on the red liquid in the dialysis bag, and obtaining solid powder which is the selenium nano-particles after freeze drying.

Example 6:

(1) adding 1 weight part of polyvinylpyrrolidone into a flask containing 14 weight parts of diethylenetriamine, ultrasonically dispersing and stirring until the polyvinylpyrrolidone is dissolved, then respectively adding 1 weight part of selenium dioxide and 1 weight part of glucose, simultaneously stirring for 30 minutes while ultrasonically dispersing, then introducing argon protective gas into the flask, placing the flask on an oil bath pot, heating to 150 ℃, and reacting for 4 hours at constant temperature to obtain a selenium solution;

(2) and (2) putting the selenium solution obtained in the step (1) into a dialysis bag with the molecular weight cutoff of 500 for dialysis for 24 hours, changing water once in the middle of the dialysis bag at intervals of 6 hours, carrying out freeze drying on red liquid in the dialysis bag after dialysis, and obtaining solid powder which is selenium nano-particles after freeze drying.

Example 7:

(1) respectively adding 1 weight part of polyvinylpyrrolidone and 0.2 weight part of selenium dioxide into a flask containing 10 weight parts of diethylenetriamine, performing ultrasonic dispersion and stirring until the polyvinylpyrrolidone and the selenium dioxide are dissolved, then adding 1 weight part of glucose, simultaneously performing ultrasonic dispersion and stirring for 30 minutes, then introducing argon protective gas into the flask, placing the flask on an oil bath pot, heating to 150 ℃, and performing constant temperature reaction for 4 hours to obtain a selenium solution;

(2) and (2) putting the selenium solution obtained in the step (1) into a dialysis bag with the molecular weight cutoff of 500 for dialysis for 24 hours, changing water once in the middle of the dialysis bag at intervals of 6 hours, carrying out freeze drying on red liquid in the dialysis bag after dialysis, and obtaining solid powder which is selenium nano-particles after freeze drying.