阅读说明：本技术 一种二硫化钨/硫化铟复合纳米材料的制备方法 (Preparation method of tungsten disulfide/indium sulfide composite nano material ) 是由 周杰 朱蓓蓓 吴斌 姜敏 周道 丁邦琴 黄徽 于 2020-06-23 设计创作，主要内容包括：本发明公开了一种二硫化钨/硫化铟复合纳米材料的制备方法,包括：(1)将六氯化钨溶于有机溶剂中,至固体完全溶解后形成溶液A；(2)将硝酸铟溶于有机溶剂中,形成溶液B；(3)将溶液B滴加至溶液A中,搅拌,加入硫代乙酰胺和二烯丙基甲基十二烷基溴化铵,120～200℃下进行溶剂热反应,得到二硫化钨/硫化铟复合纳米材料。制备步骤简单,成本低廉,有机结合了二硫化钨和硫化铟两种组分的优点,并使二者产生了光电协同作用,增强其光催化活性。(The invention discloses a preparation method of a tungsten disulfide/indium sulfide composite nano material, which comprises the following steps: (1) dissolving tungsten hexachloride in an organic solvent until the solid is completely dissolved to form a solution A; (2) dissolving indium nitrate in an organic solvent to form a solution B; (3) and dropwise adding the solution B into the solution A, stirring, adding thioacetamide and diallylmethyldidodecylammonium bromide, and carrying out solvothermal reaction at 120-200 ℃ to obtain the tungsten disulfide/indium sulfide composite nano material. The preparation method has the advantages of simple preparation steps and low cost, organically combines the advantages of the tungsten disulfide and the indium sulfide, and enables the tungsten disulfide and the indium sulfide to generate a photoelectric synergistic effect to enhance the photocatalytic activity of the tungsten disulfide and the indium sulfide.)

1. A preparation method of a tungsten disulfide/indium sulfide composite nano material is characterized by comprising the following steps:

(1) dissolving tungsten hexachloride in an organic solvent until the solid is completely dissolved to form a solution A;

(2) dissolving indium nitrate in an organic solvent to form a solution B;

(3) and dropwise adding the solution B into the solution A, stirring, adding thioacetamide and diallylmethyldidodecylammonium bromide, and carrying out solvothermal reaction at 120-200 ℃ to obtain the tungsten disulfide/indium sulfide composite nano material.

2. The method for preparing the tungsten disulfide/indium sulfide composite nanomaterial according to claim 1, wherein the molar ratio of the tungsten hexachloride to the indium nitrate is 0.025-2: 1.

3. the method for preparing the tungsten disulfide/indium sulfide composite nanomaterial according to claim 1, wherein the thioacetamide is added in a molar amount which is the sum of 3 times the molar amount of tungsten atoms and 2.25 times the molar amount of indium atoms.

4. The preparation method of the tungsten disulfide/indium sulfide composite nanomaterial according to claim 1, wherein the molar concentration of the tungsten hexachloride in the organic solvent is 0-1.5 mmol/mL;

optionally, the molar concentration of the indium nitrate in the organic solvent is 0.75-1.5 mmol/mL.

5. The method for preparing the tungsten disulfide/indium sulfide composite nanomaterial according to claim 1, wherein the molar concentration of the diallylmethyldidodecylammonium bromide is 5-20 mg/mL.

6. The method for preparing the tungsten disulfide/indium sulfide composite nanomaterial according to claim 1, wherein the organic solvent is absolute ethyl alcohol.

7. The method for preparing the tungsten disulfide/indium sulfide composite nanomaterial according to claim 1, wherein the reaction time of the solvothermal reaction is 4-48 h.

8. The preparation method of the tungsten disulfide/indium sulfide composite nanomaterial according to claim 1, wherein the method for dissolving tungsten hexachloride in the organic solvent is ultrasonic dispersion, and stirring is continued for 30 min;

optionally, the indium nitrate is dissolved in the organic solvent by stirring for 30 min.

9. The method for preparing the tungsten disulfide/indium sulfide composite nanomaterial according to claim 1, wherein the step (3) is specifically as follows:

and slowly dropwise adding the solution B into the solution A, stirring for 30min, adding thioacetamide and diallylmethyldidodecylammonium bromide, stirring for 2h, transferring to a reaction kettle with a polytetrafluoroethylene lining, and placing in an oven for solvothermal reaction.

10. The method for preparing the tungsten disulfide/indium sulfide composite nanomaterial according to claim 1, wherein the method further comprises the steps of:

(4) and centrifuging the obtained product, washing the product with deionized water and absolute ethyl alcohol for 3 times respectively, and then carrying out vacuum drying at 60 ℃ to obtain the pure tungsten disulfide/indium sulfide composite nano material.

Technical Field

The invention belongs to the technical field of preparation methods of photocatalytic materials, and particularly relates to a preparation method of a tungsten disulfide/indium sulfide composite nano material.

Background

Since the 20 th century, water pollution caused by toxic and non-degradable organic pollutants (such as halogenated substances, pesticides and dyes) causes a series of environmental problems, and environmental water pollution and air pollution become major problems influencing human life and health. Conventional water treatment methods, for example: the methods such as adsorption method, coagulation method, chemical precipitation method, membrane filtration separation, extraction and the like still have certain difficulty in actual treatment, and the treatment effect of the traditional method is not ideal. The method utilizes solar energy through a photocatalysis method, degrades macromolecular organic pollutants into environment-friendly micromolecular substances and is hopeful to become a friendly way for solving the environmental problem of water pollution in the future. The green environment-friendly technology shows unique charm and wide application prospect in the aspects of environmental protection and new energy development.

The core of the photocatalytic technology lies in the presence of a semiconductor catalyst, such as TiO₂ZnO and the like are generally concerned by broad scholars in recent 20 years and are developed greatly. In addition to such metal oxides as semiconductor materials, sulfide semiconductor materials have very unique optical and electrical properties as wide band gap semiconductor nanomaterials, and thus are widely used In photocatalysis, photodiodes, photoconductive detectors, solar cells, solar selective coatings and sensors, such as ZnS, CdS, GaS, In₂S₃，WS₂And the like. Among them, In₂S₃And WS₂Due to its unique forbidden band width and visible light response characteristics, it has become a hot point of research.

Indium sulfide (In)₂S₃) Is one of the important sulfides in group III-VI A, and is an important semiconductor material, and the semiconductor material generally has three crystalline structures: alpha-In₂S₃，β-In₂S₃，γ-In₂S₃. Wherein beta-In₂S₃The material is an intrinsic n-type semiconductor material, the forbidden band width of the material is about 2eV, and the material is most widely applied. In the last decade, nanostructured materials with different morphologies and structures have been widely reported, and their applications in the fields of solar cells, optical waveguides, lithium ion batteries, photocatalysis, etc. have received attention from many groups of subjects. The reported morphologies at present include nanoparticles, nanowires with one-dimensional structures, nanorods and nanotubes, nanosheets with two-dimensional structures, and three-dimensional-structure nanoflowers or nanosphere spheres assembled by nanoparticles or nanosheets. Recently, Xing et al (J Colloid Interf Sci,2014,433(1):9-15) have introduced In₂S₃And g-C₃N₄In with high photocatalytic activity is compositely prepared₂S₃/g-C₃N₄The rhodamine B can be effectively degraded by the heterojunction under visible light. Yan et al (ApplCatal B-Environ,2017,202:84-94) with small amounts of Ag₃PO₄Modified In₂S₃Remarkably improve In₂S₃The activity of (2) can efficiently degrade organic pollutants. However, the synthesis method provided by the modification is complex and harsh, and is not suitable for mass production.

Tungsten disulfide is a transition metal disulfide compound with a layered structure similar to graphite, and has a hexagonal close-packed layered structure. Tungsten disulfide has good high temperature resistance and excellent lubricating property, and also has good catalytic performance, such as being used as a carrier of hydrodesulfurization. As an indirect semiconductor, tungsten disulfide is also an excellent semiconductor material with a band gap much smaller than that of TiO₂Under the irradiation of visible light, photons can be absorbed to generate electron-hole pairs, and the method has important application in the aspects of organic matter degradation and hydrogen production by water photolysis. Chinese patent 201510287069.1 discloses a preparation method of a tungsten disulfide-activated carbon composite material, which is used as an electrode material of a super capacitor. Chinese patent 201510416849.1 discloses a tungsten disulfide/titanium dioxide composite and a method for preparing the same, which can be used as a lubricant or a photocatalyst.

Hitherto, no report has been found on the one-step preparation of the tungsten disulfide/indium sulfide composite nanomaterial by adopting a solvothermal method, and the tungsten disulfide/indium sulfide composite nanomaterial organically combines the advantages of two components, namely tungsten disulfide and indium sulfide, and the tungsten disulfide/indium sulfide composite nanomaterial generates a photoelectric synergistic effect to enhance the photocatalytic activity of the tungsten disulfide and indium sulfide, so that the development of the tungsten disulfide/indium sulfide composite nanomaterial has a wide application prospect.

Disclosure of Invention

Aiming at the problems in the background art, the invention provides a preparation method of a tungsten disulfide/indium sulfide composite nano material with excellent performance, the preparation method has simple steps and low cost, organically combines the advantages of two components of tungsten disulfide and indium sulfide, and leads the tungsten disulfide and the indium sulfide to generate photoelectric synergistic effect to enhance the photocatalytic activity of the tungsten disulfide/indium sulfide composite nano material.

In order to achieve the purpose, the invention provides the following technical scheme:

a preparation method of a tungsten disulfide/indium sulfide composite nano material comprises the following steps:

(1) dissolving tungsten hexachloride in an organic solvent until the solid is completely dissolved to form a solution A;

(2) dissolving indium nitrate in an organic solvent to form a solution B;

(3) and dropwise adding the solution B into the solution A, stirring, adding thioacetamide and diallylmethyldidodecylammonium bromide, and carrying out solvothermal reaction at 120-200 ℃ to obtain the tungsten disulfide/indium sulfide composite nano material.

In a preferable embodiment, the molar ratio of the tungsten hexachloride to the indium nitrate is 0.025-2: 1.

as a preferable mode, the thioacetamide is added in a molar ratio of 3 times the molar ratio of the tungsten atom to 2.25 times the molar ratio of the indium atom.

As a preferable scheme, the molar concentration of the tungsten hexachloride in the organic solvent is 0.75-1.5 mmol/mL;

optionally, the molar concentration of the indium nitrate in the organic solvent is 0-1.5 mmol/mL.

Preferably, the molar concentration of the diallylmethyldidodecylammonium bromide is 5-20 mg/mL.

In a preferred embodiment, the organic solvent is absolute ethyl alcohol.

The organic solvent is not limited to absolute ethyl alcohol, and any organic solvent capable of dissolving tungsten hexachloride and indium nitrate may be used, and those skilled in the art can freely select the organic solvent as needed.

Preferably, the reaction time of the solvothermal reaction is 4-48 h.

As a preferable scheme, the method for dissolving the tungsten hexachloride in the organic solvent is ultrasonic dispersion, and stirring is continued for 30 min;

optionally, the indium nitrate is dissolved in the organic solvent by stirring for 30 min.

As a preferable scheme, the step (3) is specifically as follows:

and slowly dropwise adding the solution B into the solution A, stirring for 30min, adding thioacetamide and diallylmethyldidodecylammonium bromide, stirring for 2h, transferring to a reaction kettle with a polytetrafluoroethylene lining, and placing in an oven for solvothermal reaction. Wherein the purpose of placing in an oven is to provide a reaction temperature of 120-200 ℃.

As a preferred embodiment, the preparation method further comprises the following steps:

(4) and centrifuging the obtained product, washing the product with deionized water and absolute ethyl alcohol for 3 times respectively, and then carrying out vacuum drying at 60 ℃ to obtain the pure tungsten disulfide/indium sulfide composite nano material.

The term "solvothermal reaction" used in the present invention refers to a method for synthesizing a heterogeneous phase nano material in a closed container with a solvent as a reaction medium at high temperature and high pressure, which is one of wet chemical methods for preparing powder. The method ensures that nitrogen is not easy to lose and can ensure reasonable carbon-nitrogen atom ratio.

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

(1) the invention prepares the tungsten disulfide/indium sulfide composite nano material by one step through a solvothermal method for the first time, has simple preparation process and is suitable for mass production. The process of firstly synthesizing tungsten disulfide and indium sulfide respectively and then physically compounding is avoided, so that the tungsten disulfide and the indium sulfide enter the crystal structure of the other side, the tungsten disulfide and the indium sulfide can have sufficient dispersibility, the electron transfer capacity is improved, and the catalytic performance is improved.

(2) The composite nano material prepared by the invention combines the advantages of tungsten disulfide and indium sulfide, fully exerts the excellent performances of the tungsten disulfide and the indium sulfide, and has wider application in known or unknown fields.

Drawings

Figure 1 is an XRD pattern of the tungsten disulfide/indium sulfide composite nanomaterial prepared in example 1.

Detailed Description

The following examples are given to illustrate specific embodiments of the present invention in detail. The following examples are intended to illustrate the invention but are not intended to limit the scope of the invention.