阅读说明：本技术 一种串珠状硫化铜颗粒的制备方法及其应用 (Preparation method and application of beaded copper sulfide particles ) 是由 刘晓伟 杨宝朔 商继涛 艾远 于 2021-10-28 设计创作，主要内容包括：本发明涉及硫化铜材料制备方法的技术领域,具体涉及一种串珠状硫化铜颗粒的制备方法及其应用,包括如下步骤：将铜盐和硫代硫酸钠加入水和无水乙醇的混合溶剂中,搅拌至溶解完全；将所得溶液在60～140℃下的多个阶梯温度下分别反应一定时间,得到硫化铜黑色沉淀；对所得的黑色沉淀进行震荡、洗涤、离心后干燥,得到所述串珠状硫化铜颗粒。本发明的串珠状硫化铜颗粒及其制备方法,通过控制铜盐与硫代硫酸钠的分阶段加热反应制备了球形颗粒组装的串珠状的硫化铜颗粒。同时具备流程简单、无添加剂、反应周期短且一次完成、成本低、易于规模化生产、适合工业推广与应用等优点。(The invention relates to the technical field of copper sulfide material preparation methods, in particular to a preparation method and application of beaded copper sulfide particles, and the preparation method comprises the following steps: adding copper salt and sodium thiosulfate into a mixed solvent of water and absolute ethyl alcohol, and stirring until the copper salt and the sodium thiosulfate are completely dissolved; respectively reacting the obtained solution at a plurality of step temperatures of 60-140 ℃ for a certain time to obtain black copper sulfide precipitates; and vibrating, washing, centrifuging and drying the obtained black precipitate to obtain the beaded copper sulfide particles. The beaded copper sulfide particles assembled by spherical particles are prepared by controlling the staged heating reaction of copper salt and sodium thiosulfate. Meanwhile, the method has the advantages of simple flow, no additive, short reaction period, one-time completion, low cost, easiness in large-scale production, suitability for industrial popularization and application and the like.)

1. A preparation method of beaded copper sulfide particles is characterized by comprising the following steps:

step S1: adding copper salt and sodium thiosulfate into a mixed solvent of water and absolute ethyl alcohol, and stirring until the copper salt and the sodium thiosulfate are completely dissolved;

step S2: respectively reacting the solution obtained in the step S1 at a plurality of step temperatures of 60-140 ℃ for a certain time to obtain black copper sulfide precipitate;

step S3: and (4) oscillating, washing, centrifuging and drying the black precipitate obtained in the step S2 to obtain the beaded copper sulfide particles.

2. The method of producing beaded copper sulfide particles of claim 1, wherein: in the step S1, the copper salt is any one of copper sulfate, copper nitrate, copper chloride, and copper carbonate.

3. The method of producing beaded copper sulfide particles of claim 1, wherein: in the step S1, the volume ratio of water to absolute ethyl alcohol is (1-10): 1.

4. the method of producing beaded copper sulfide particles of claim 1, wherein: in step S2, the temperature is maintained in 3 steps, which are: the first step is 60-80 ℃, the second step is 90-110 ℃, and the third step is 120-140 ℃.

5. The method of producing beaded copper sulfide particles of claim 4, wherein: in the step S2, the total reaction time is 1-2h, wherein the first step temperature reaction time is less than or equal to the second step temperature reaction time and is less than or equal to the third step temperature reaction time.

6. The method of producing beaded copper sulfide particles of claim 1, wherein: in the step S3, the centrifugal separation condition is 4000-5000 r/min, and the centrifugal time is 0.5-1 min.

7. The method of producing beaded copper sulfide particles of claim 1, wherein: in the step S3, the drying temperature is not higher than 70 ℃.

8. The method of producing beaded copper sulfide particles of claim 1, wherein: in the step S3, the prepared copper sulfide particles have a bead-like morphology with spherical particle assemblies.

9. Application of the beaded copper sulfide particles prepared by the preparation method of any one of claims 1 to 8 in the field of photocatalysis.

Technical Field

The invention relates to the technical field of copper sulfide material preparation methods, in particular to a preparation method and application of beaded copper sulfide particles.

Background

Copper sulfide is an important transition metal sulfide, is black brown, has excellent light, electricity, catalysis and other characteristics, and has wide application prospect in the fields of photocatalyst, solar cell, nonlinear optics, super capacitor, photothermal therapy and the like.

Since copper sulfide particles of different sizes, shapes and structures have performance performances of different degrees, the improvement of specific surface area and porosity is one of the main ways to further improve the performance. At present, copper sulfide particles with various shapes such as tubular shapes, rod shapes, linear shapes, spherical shapes and the like are successfully synthesized, but particles with special structures are still to be further explored. Meanwhile, the preparation methods are also reported in hydrothermal methods, solvothermal methods and the like, and are dangerous due to the need of high-temperature and high-pressure environments or harsh equipment conditions, and long in time consumption due to the need of additives or templates.

Therefore, the development of a preparation method of the beaded copper sulfide particles, which is simple and efficient, has low requirements on environment and equipment, mild conditions, strong controllability and easy realization of large-scale industrial production, is of great significance.

Disclosure of Invention

One of the purposes of the invention is to provide a preparation method of beaded copper sulfide particles, which has the advantages of simple process, no additive, short period, low cost, easy large-scale production and the like.

The invention also aims to provide application of the beaded copper sulfide particles.

The scheme adopted by the invention for realizing one of the purposes is as follows: a preparation method of beaded copper sulfide particles comprises the following steps:

step S1: adding copper salt and sodium thiosulfate into a mixed solvent of water and absolute ethyl alcohol, and stirring until the copper salt and the sodium thiosulfate are completely dissolved;

step S2: respectively reacting the solution obtained in the step S1 at a plurality of step temperatures of 60-140 ℃ for a certain time to obtain black copper sulfide precipitate;

step S3: and (4) oscillating, washing, centrifuging and drying the black precipitate obtained in the step S2 to obtain the beaded copper sulfide particles.

Preferably, in step S1, the copper salt is any one of copper sulfate, copper nitrate, copper chloride and copper carbonate.

Preferably, in the step S1, the volume ratio of water to absolute ethyl alcohol is (1-10): 1.

preferably, in step S2, the temperature is maintained in 3 steps, which are: the first step is 60-80 ℃, the second step is 90-110 ℃, and the third step is 120-140 ℃.

Preferably, in the step S2, the total reaction time is 1-2h, wherein the first step temperature reaction time is less than or equal to the second step temperature reaction time is less than or equal to the third step temperature reaction time.

Preferably, in the step S3, the centrifugal separation condition is 4000 to 5000r/min, and the centrifugal time is 0.5 to 1 min.

Preferably, in the step S3, the drying temperature is not higher than 70 ℃.

Preferably, in the step S3, the prepared copper sulfide particles have a bead-like morphology of spherical particle assembly.

The second scheme adopted by the invention for achieving the purpose is as follows: the beaded copper sulfide particles prepared by the preparation method are applied to the field of photocatalysis.

The invention has the following advantages and beneficial effects:

the beaded copper sulfide particles assembled by spherical particles are prepared by controlling the staged heating reaction of copper salt and sodium thiosulfate. Meanwhile, the method has the advantages of simple flow, no additive, short reaction period, one-time completion, low cost, easiness in large-scale production, suitability for industrial popularization and application and the like.

The novel beaded copper sulfide particle prepared by the preparation method is formed by sequentially assembling spherical units with the particle size of 50-200 nm, and the whole bead has a non-straight curled structure, so that the specific surface area and the porosity of the copper sulfide particle are further improved.

The beaded copper sulfide particles prepared by the preparation method can be applied to the field of photocatalysis.

Drawings

FIG. 1 is a scanning electron micrograph of spherical particle-assembled beaded copper sulfide particles prepared in example 1;

FIG. 2 is a scanning electron micrograph of spherical particle-assembled beaded copper sulfide particles prepared in example 4;

FIG. 3 is a scanning electron micrograph of spherical copper sulfide particles prepared in comparative example 1;

FIG. 4 is a scanning electron micrograph of spherical particle agglomerate copper sulfide particles prepared in comparative example 2;

FIG. 5 is a scanning electron micrograph of spherical copper sulfide particles prepared in comparative example 3;

FIG. 6 is a scanning electron micrograph of non-spherical copper sulfide particles prepared in comparative example 4;

fig. 7 is a scanning electron micrograph of non-spherical particle-assembled linear copper sulfide particles prepared in comparative example 5.

Detailed Description

The following examples are provided to further illustrate the present invention for better understanding, but the present invention is not limited to the following examples.

Example 1

Step S1: adding copper salt and sodium thiosulfate into a mixed solvent of water and absolute ethyl alcohol, and stirring until the copper salt and the sodium thiosulfate are completely dissolved;

step S2: sequentially carrying out stage reaction on the solution at 60-140 ℃ for increasing time at 3 step temperatures to obtain black copper sulfide precipitate;

step S3: sequentially adopting water, ethanol and acetone to respectively shake, wash and centrifuge the black precipitate so as to remove byproducts;

step S4: and keeping the temperature at 60 ℃ for 0.7h, drying and precipitating to obtain copper sulfide particles.

According to the steps, wherein the copper salt is copper sulfate, and the volume ratio of water to absolute ethyl alcohol is further 5: 1, 3 temperatures are respectively: the temperature of 60 ℃, 100 ℃, 130 ℃, the reaction time is 1.5h totally, the reaction time is 0.4h at 60 ℃, the reaction time is 0.5h at 100 ℃, the reaction time is 0.6h at 130 ℃, the centrifugal separation condition is 4000-5000 r/min, 0.5-1 min, the drying environment is a common vacuum drying oven, and the prepared copper sulfide particles have a bead-like shape assembled by spherical particles.

FIG. 1 is a scanning electron microscope image of beaded copper sulfide particles assembled from spherical particles prepared in example 1, from which it can be seen that many spherical particles are sequentially connected to form beads, and the particle diameter of a single spherical particle is 200nm or less.

Example 2

Step S1: adding copper salt and sodium thiosulfate into a mixed solvent of water and absolute ethyl alcohol, and stirring until the copper salt and the sodium thiosulfate are completely dissolved;

step S2: sequentially carrying out time-increasing stage reaction on the solution at 60-140 ℃ at 3 step temperatures to obtain black copper sulfide precipitate;

step S3: sequentially adopting water, ethanol and acetone to respectively shake, wash and centrifuge the black precipitate so as to remove byproducts;

step S4: and keeping the temperature at 70 ℃ for 0.7h, drying and precipitating to obtain copper sulfide particles.

According to the steps, wherein the copper salt is copper nitrate, and the volume ratio of water to absolute ethyl alcohol is further 1: 1, 3 temperature intervals are respectively: the temperature of 70 ℃, the temperature of 90 ℃, the temperature of 120 ℃, the reaction time of 1 hour, the temperature of 70 ℃ for 0.2 hour, the temperature of 90 ℃ for 0.3 hour and the temperature of 120 ℃ for 0.5 hour, the centrifugal separation conditions are 4000-5000 r/min and 0.5-1 min, the drying environment is a common vacuum drying oven, and the prepared copper sulfide particles have a beaded shape assembled by spherical particles and are similar to the appearance of an electron microscope picture shown in attached figure 1.

Example 3

Step S1: adding copper salt and sodium thiosulfate into a mixed solvent of water and absolute ethyl alcohol, and stirring until the copper salt and the sodium thiosulfate are completely dissolved;

step S2: sequentially carrying out stage reaction on the solution at 60-140 ℃ for increasing time at 3 step temperatures to obtain black copper sulfide precipitate;

step S3: sequentially adopting water, ethanol and acetone to respectively shake, wash and centrifuge the black precipitate so as to remove byproducts;

step S4: and keeping the temperature at 50 ℃ for 0.7h, drying and precipitating to obtain copper sulfide particles.

According to the steps, wherein the copper salt is copper chloride, and the volume ratio of water to absolute ethyl alcohol is further 10: 1, 3 temperature intervals are respectively: the temperature is 80 ℃, the temperature is 110 ℃, the temperature is 140 ℃, the reaction time is 2 hours, namely, the reaction time is 0.5 hour at 80 ℃, the reaction time is 0.7 hour at 110 ℃, the reaction time is 0.8 hour at 140 ℃, the centrifugal separation condition is 4000-5000 r/min and 0.5-1 min, the drying environment is a common vacuum drying oven, and the prepared copper sulfide particles have a beaded shape assembled by spherical particles and are similar to the appearance of an electron microscope picture shown in attached figure 1.

Example 4

Step S1: adding copper salt and sodium thiosulfate into a mixed solvent of water and absolute ethyl alcohol, and stirring until the copper salt and the sodium thiosulfate are completely dissolved;

step S2: sequentially carrying out stage reactions on the solution at 60-140 ℃ for 3 step temperatures for equal time to obtain black copper sulfide precipitates;

step S3: sequentially adopting water, ethanol and acetone to respectively shake, wash and centrifuge the black precipitate so as to remove byproducts;

step S4: and keeping the temperature at 60 ℃ for 0.7h, drying and precipitating to obtain copper sulfide particles.

According to the steps, wherein the copper salt is copper sulfate, and the volume ratio of water to absolute ethyl alcohol is 5: 1, 3 temperatures are respectively: the temperature of 60 ℃, 100 ℃, 130 ℃, the reaction time is 1.5h, the reaction time is 0.5h at 60 ℃, the reaction time is 0.5h at 100 ℃, the reaction time is 0.5h at 130 ℃, the centrifugal separation condition is 4000-5000 r/min and 0.5-1 min, the drying environment is a common vacuum drying oven, and the prepared copper sulfide particles have a bead-like shape assembled by spherical particles.

FIG. 2 is a scanning electron micrograph of beaded copper sulfide particles assembled from spherical particles prepared in example 4, in which a plurality of spherical particles are sequentially connected to form a bead-like structure much shorter than that of example 1, and the particle diameters of the individual spherical particles are further reduced to below 100 nm.

Comparative example 1

Step S1: adding copper salt and sodium thiosulfate into a mixed solvent of water and absolute ethyl alcohol, and stirring until the copper salt and the sodium thiosulfate are completely dissolved;

step S2: carrying out reaction on the solution at 60 ℃ for 1.5h to obtain black copper sulfide precipitate;

step S3: sequentially adopting water, ethanol and acetone to respectively shake, wash and centrifuge the black precipitate so as to remove byproducts;

step S4: and keeping the temperature at 60 ℃ for 0.7h, drying and precipitating to obtain copper sulfide particles.

According to the steps, wherein the copper salt is copper sulfate, and the volume ratio of water to absolute ethyl alcohol is 5: 1, the centrifugal separation conditions are 4000-5000 r/min and 0.5-1 min, the drying environment is a common vacuum drying oven, and the prepared copper sulfide particles have a spherical particle shape.

FIG. 3 is a scanning electron microscope image of spherical copper sulfide particles prepared in comparative example 1, which are composed of two kinds of spherical particles having a large particle diameter of 1 to 1.5 μm and a small particle diameter of 300 to 500nm, and the small particles attached to the large particles lay a foundation for the formation of agglomerates.

Comparative example 2

Step S1: adding copper salt and sodium thiosulfate into a mixed solvent of water and absolute ethyl alcohol, and stirring until the copper salt and the sodium thiosulfate are completely dissolved;

step S2: sequentially carrying out time-increasing staged reaction on the solution at the temperature of 60-110 ℃ at 2 step temperatures to obtain black copper sulfide precipitate;

step S3: sequentially adopting water, ethanol and acetone to respectively shake, wash and centrifuge the black precipitate so as to remove byproducts;

step S4: and keeping the temperature at 60 ℃ for 0.7h, drying and precipitating to obtain copper sulfide particles.

According to the steps, wherein the copper salt is copper sulfate, and the volume ratio of water to absolute ethyl alcohol is 5: 1, 2 temperatures are respectively: the temperature is 60 ℃, the temperature is 100 ℃, the reaction time is 1.5h totally, namely, the reaction is 0.7h at 60 ℃, the reaction is 0.8h at 100 ℃, the centrifugal separation condition is 4000-5000 r/min and 0.5-1 min, the drying environment is a common vacuum drying oven, and the prepared copper sulfide particles have the form of spherical particle aggregates.

FIG. 4 is a scanning electron micrograph of spherical particle agglomerate copper sulfide particles prepared in comparative example 2, in which a plurality of spherical particles are agglomerated and the particle size of individual spherical particles is reduced to 500nm or less.

Comparative example 3

Step S1: adding copper salt and sodium thiosulfate into a mixed solvent of water and absolute ethyl alcohol, and stirring until the copper salt and the sodium thiosulfate are completely dissolved;

step S2: carrying out reaction on the solution at 100 ℃ for 1.5h to obtain black copper sulfide precipitate;

step S3: sequentially adopting water, ethanol and acetone to respectively shake, wash and centrifuge the black precipitate so as to remove byproducts;

step S4: and keeping the temperature at 60 ℃ for 0.7h, drying and precipitating to obtain copper sulfide particles.

According to the steps, wherein the copper salt is copper sulfate, and the volume ratio of water to absolute ethyl alcohol is 5: 1, the centrifugal separation conditions are 4000-5000 r/min and 0.5-1 min, the drying environment is a common vacuum drying oven, and the prepared copper sulfide particles have the shape of spherical particle aggregates.

FIG. 5 is a scanning electron micrograph of spherical copper sulfide particles prepared in comparative example 3, which are composed of two kinds of spherical particles having a large particle diameter of 0.7 to 1 μm and a small particle diameter of 200 to 300 nm.

Comparative example 4

Step S1: adding copper salt and sodium thiosulfate into a mixed solvent of water and absolute ethyl alcohol, and stirring until the copper salt and the sodium thiosulfate are completely dissolved;

step S2: carrying out reaction on the solution at 50 ℃ for 1.5h to obtain black copper sulfide precipitate;

step S3: sequentially adopting water, ethanol and acetone to respectively shake, wash and centrifuge the black precipitate so as to remove byproducts;

step S4: and keeping the temperature at 60 ℃ for 0.7h, drying and precipitating to obtain copper sulfide particles.

According to the steps, wherein the copper salt is copper sulfate, and the volume ratio of water to absolute ethyl alcohol is 5: 1, the centrifugal separation conditions are 4000-5000 r/min and 0.5-1 min, the drying environment is a common vacuum drying oven, and the prepared copper sulfide particles have a non-spherical particle shape.

FIG. 6 is a scanning electron micrograph of non-spherical copper sulfide particles prepared in comparative example 4, which failed to form a spherical particle morphology due to a reaction temperature of 50 ℃ lower than the temperature range specified in the present invention.

Comparative example 5

Step S1: adding copper salt and sodium thiosulfate into a mixed solvent of water and absolute ethyl alcohol, and stirring until the copper salt and the sodium thiosulfate are completely dissolved;

step S2: carrying out reaction on the solution at 150 ℃ for 1.5h to obtain black copper sulfide precipitate;

step S3: sequentially adopting water, ethanol and acetone to respectively shake, wash and centrifuge the black precipitate so as to remove byproducts;

step S4: and keeping the temperature at 60 ℃ for 0.7h, drying and precipitating to obtain copper sulfide particles.

According to the steps, wherein the copper salt is copper sulfate, and the volume ratio of water to absolute ethyl alcohol is 5: 1, the centrifugal separation condition is 4500r/min and 0.7min, the drying environment is a common vacuum drying oven, and the prepared copper sulfide particles have a linear shape formed by assembling non-spherical particles.

FIG. 7 is a scanning electron microscope photograph of non-spherical particle-assembled linear copper sulfide particles prepared in comparative example 5, which also failed to form spherical particles due to the reaction temperature of 150 ℃ being higher than the temperature range specified in the present invention, but also resulted in particle-assembled linear structures.

The only differences between the different examples and comparative examples are the reaction temperature and whether there are time-escalating, staged temperatures. The 3 reaction temperature stages and the increasing time of examples 1-3, all within the specified range of the present invention, resulted in beaded copper sulfide particles assembled from spherical particles, while the 43 reaction temperature stages in example were equally timed, and beaded copper sulfide particles assembled from spherical particles were also prepared, and the combination of 3 staged temperatures and times was found to be deficient in the formation of beaded structures in combination with the smaller particle size agglomerates and beaded structures obtained from comparative examples 1, 2, 3, not the 3-stage reaction temperatures.

Combining the non-staged reaction temperatures of 50 ℃ and 150 ℃ of comparative examples 4 and 5 with the resulting non-spherical particle product, it can be seen that spherical structures are only obtained within the appropriate temperature staging ranges set forth in the present invention.

It should be noted that, according to the implementation requirement, each step described in the present application can be divided into more steps, and two or more steps or partial operations of the steps can be combined into a new step to achieve the purpose of the present invention.

It should be understood that parts of the specification not set forth in detail are well within the prior art.

While the foregoing is directed to the preferred embodiment of the present invention, other and further embodiments of the invention may be devised without departing from the basic scope thereof, and the scope thereof is determined by the claims that follow.