CN112811469A - Preparation method of single-layer or few-layer tungsten disulfide nano material - Google Patents

Preparation method of single-layer or few-layer tungsten disulfide nano material Download PDF

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CN112811469A
CN112811469A CN202110277826.2A CN202110277826A CN112811469A CN 112811469 A CN112811469 A CN 112811469A CN 202110277826 A CN202110277826 A CN 202110277826A CN 112811469 A CN112811469 A CN 112811469A
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few
nano material
tungsten disulfide
disulfide nano
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CN112811469B (en
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黄剑锋
罗晓敏
曹丽云
李嘉胤
王瑜航
魏世英
李心诚
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Shaanxi University of Science and Technology
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G41/00—Compounds of tungsten
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/20—Two-dimensional structures
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
    • C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/01—Particle morphology depicted by an image
    • C01P2004/03—Particle morphology depicted by an image obtained by SEM
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/01—Particle morphology depicted by an image
    • C01P2004/04—Particle morphology depicted by an image obtained by TEM, STEM, STM or AFM

Abstract

A preparation method of a single-layer or few-layer tungsten disulfide nano material comprises the steps of adding tungsten hexachloride into an ethanol solution, and magnetically stirring until the tungsten hexachloride is completely dissolved to form a yellow clear solution A; adding thioacetamide into the solution A, and uniformly stirring to form a mixed solution; transferring the mixed solution to a polytetrafluoroethylene reaction kettle for homogeneous reaction, and naturally cooling to room temperature after the reaction is finished; and taking out the product, washing the product by using absolute ethyl alcohol and deionized water in sequence, carrying out centrifugal separation, and then carrying out freeze drying to obtain the single-layer or few-layer tungsten disulfide nano material. The invention avoids the traditional stripping means or prepares the tungsten disulfide nano material with a single layer or less layers under complex process conditions. The single-layer or few-layer tungsten disulfide nano material is prepared by controlling the reaction time by utilizing the low-temperature solvothermal reaction, and has more active sites and larger specific surface area. The method provides another idea for efficiently and simply preparing the single-layer or few-layer tungsten disulfide nano material.

Description

Preparation method of single-layer or few-layer tungsten disulfide nano material
Technical Field
The invention relates to the technical field of preparation of tungsten disulfide nano materials, in particular to a preparation method of a single-layer or few-layer tungsten disulfide nano material.
Background
The two-dimensional layered nano-material mainly comprises graphene, a two-dimensional transition metal sulfur compound and the like. The two-dimensional transition metal sulfide is mainly connected between layers through Van der Waals force, and the acting force is relatively weak, so that the layers are easy to peel off to form a nano lamellar structure. The two-dimensional transition metal sulfide is of a layered structure and exists in a form of X-M-X, and chalcogen atoms are separated by transition metal atoms to form a sandwich structure. By virtue of the special structure, a large amount of transition metal sulfides appear in the fields of energy, environmental protection, mechanical friction, biomedicine and the like. The transition metal tungsten sulfide nano material is currently held by researchers, and particularly is mainly a nano sheet of molybdenum disulfide and tungsten disulfide. Single or few layers of tungsten disulfide are favored by researchers because of their more active sites and larger specific surface area.
Currently reported single-layer or few-layer WS2The preparation method of the nano material mainly comprises a liquid phase ultrasonic stripping method, mainly comprises the steps of further collecting and precipitating tungsten disulfide powder after ultrasonic treatment, and repeatedly collecting the stripped tungsten disulfide nano material for many times, obviously, the method has low efficiency. In addition, it has been reported that (NH) is utilized by a method of electrospinning and pyrolysis4)2WS4However, the process is very complicated and is not suitable for large-scale process preparation.
Disclosure of Invention
The invention aims to provide a simple preparation method for synthesizing a single-layer or few-layer tungsten disulfide nano material by using a low-temperature liquid phase.
In order to achieve the purpose, the invention adopts the technical scheme that:
the method comprises the following steps: adding 2.38-4.76 g of tungsten hexachloride into 30-60 mL of ethanol solution, and magnetically stirring until the tungsten hexachloride is completely dissolved to form a yellow clear solution A;
step two: adding 2.25-9.02 g of thioacetamide into the solution A, and uniformly stirring to form a mixed solution;
step three: transferring the mixed solution to a 100mL polytetrafluoroethylene reaction kettle for carrying out homogeneous reaction at the reaction temperature of 120-160 ℃ for 4-24 h, and naturally cooling to room temperature after the reaction is finished;
step four: and opening the reaction kettle, taking out the product, washing the product by using absolute ethyl alcohol and deionized water in sequence, centrifugally separating the product, and drying the product in a freeze dryer at the temperature of between 40 ℃ below zero and 70 ℃ below zero and the vacuum degree of 10 to 40Pa to obtain the single-layer or few-layer tungsten disulfide nano material.
The concentration of the tungsten hexachloride in the step is 0.2 mol/L.
In the first step, the magnetic stirring speed is 300-800 r/min, and the stirring time is 15-60 min.
The molar ratio of thioacetamide to tungsten hexachloride added in the second step is 5-10: 1.
and step four, repeatedly washing the mixture for 4-6 times by adopting absolute ethyl alcohol and deionized water.
The invention avoids the traditional stripping means or prepares the tungsten disulfide nano material with a single layer or less layers under complex process conditions, and the tungsten disulfide nano material has more active sites and larger specific surface area. The method provides another idea for efficiently and simply preparing the single-layer or few-layer tungsten disulfide nano material.
Drawings
Figure 1 is an X-ray diffraction (XRD) pattern of a single or few layer tungsten disulfide nanomaterial prepared in example 3 of the present invention.
Fig. 2 is a Scanning Electron Microscope (SEM) photograph of a single layer or a few layers of tungsten disulfide nano material prepared in example 3 of the present invention.
Fig. 3 is a High Resolution Transmission Electron Microscope (HRTEM) photograph of a single layer or few layers of tungsten disulfide nanomaterial prepared in example 3 of the present invention.
The specific implementation mode is as follows:
example 1
The method comprises the following steps: adding 4.76g of tungsten hexachloride into 60mL of ethanol solution, and magnetically stirring until the tungsten hexachloride is completely dissolved to form a yellow clear solution A, wherein the stirring speed is 800r/min, and the stirring time is 60 min;
step two: adding 9.02g of thioacetamide into the solution A, and uniformly stirring to form a uniform mixed solution;
step three: transferring the solution to a 100mL polytetrafluoroethylene reaction kettle for carrying out homogeneous reaction at 160 ℃ for 24h, and naturally cooling to room temperature after the reaction is finished;
step four: and opening the reaction kettle, taking out a product, washing the product by using absolute ethyl alcohol and deionized water in sequence, performing centrifugal separation, repeatedly washing the product for 6 times, and drying the product in a freeze dryer at the temperature of-70 ℃ and the vacuum degree of 40Pa to obtain black powder, namely the single-layer or few-layer tungsten disulfide nano material.
Example 2
The method comprises the following steps: adding 2.38g of tungsten hexachloride into 30mL of ethanol solution, and magnetically stirring until the tungsten hexachloride is completely dissolved to form a yellow clear solution A, wherein the stirring speed is 300r/min, and the stirring time is 15 min;
step two: adding 2.25g of thioacetamide into the solution A, and stirring to form a uniform mixed solution;
step three: and transferring the solution to a 100mL polytetrafluoroethylene reaction kettle for homogeneous reaction, wherein the reaction temperature is 120 ℃, the reaction time is 4 hours, and naturally cooling to room temperature after the reaction is finished.
Step four: and opening the reaction kettle, taking out a product, washing the product by using absolute ethyl alcohol and deionized water in sequence, performing centrifugal separation, repeatedly washing for 4 times, and drying in a freeze dryer at the temperature of-40 ℃ and the vacuum degree of 10Pa to obtain black powder, namely the single-layer or few-layer tungsten disulfide nano material.
Example 3
The method comprises the following steps: adding 4.76g of tungsten hexachloride into 60mL of ethanol solution, and magnetically stirring until the tungsten hexachloride is completely dissolved to form a yellow clear solution A, wherein the stirring speed is 800r/min, and the stirring time is 60 min;
step two: adding 4.50g of thioacetamide into the solution A, and stirring to form a uniform mixed solution;
step three: transferring the solution to a 100mL polytetrafluoroethylene reaction kettle for carrying out homogeneous reaction at 160 ℃ for 24h, and naturally cooling to room temperature after the reaction is finished;
step four: and opening the reaction kettle, taking out a product, washing the product by using absolute ethyl alcohol and deionized water in sequence, performing centrifugal separation, repeatedly washing the product for 6 times, and drying the product in a freeze dryer at the temperature of-40 ℃ and the vacuum degree of 30Pa to obtain black powder, namely the single-layer or few-layer tungsten disulfide nano material.
Figure 1 is an X-ray diffraction (XRD) pattern of the tungsten disulfide material, single or few layer, as prepared in example 3. The sample has the same structure with the tungsten disulfide of a hexagonal system with JCPDS serial numbers of 08-0237, which shows that the tungsten disulfide prepared by the method has higher purity and no other impurity phase exists.
Figure 2 is a Scanning Electron Microscope (SEM) image of the tungsten disulfide material of single or few layers prepared in example 3. It can be seen that the surface is very smooth.
Figure 3 is a High Resolution Transmission Electron Microscope (HRTEM) photograph of a single or few layer of tungsten disulfide material prepared in example 3. The presence of a single or few layers of tungsten disulphide nanosheets can be clearly seen, with an interlayer spacing of about 0.62nm corresponding to the tungsten disulphide (002) crystal plane, consistent with the results obtained by XRD.
The invention provides a simple method for preparing a single-layer or few-layer tungsten disulfide nano material at low temperature. The method has the advantages that the single-layer or few-layer tungsten disulfide nano material can be prepared by avoiding the traditional stripping means or complicated process conditions, and the tungsten disulfide nano material has more active sites and larger specific surface area. The method provides another idea for efficiently and simply preparing the single-layer or few-layer tungsten disulfide nano material. The preparation method is simple and easy to operate, the process parameters are easy to control, the application range is wide, the reaction time is greatly shortened, the reaction efficiency is improved, the repeatability is high, and the yield is high.
Example 4
The method comprises the following steps: adding 3.97g of tungsten hexachloride into 50mL of ethanol solution, and magnetically stirring until the tungsten hexachloride is completely dissolved to form a yellow clear solution A, wherein the stirring speed is 500r/min, and the stirring time is 30 min;
step two: adding 6.01g of thioacetamide into the solution A, and stirring to form a uniform mixed solution;
step three: transferring the solution to a 100mL polytetrafluoroethylene reaction kettle for homogeneous reaction, wherein the reaction temperature is 140 ℃, the reaction time is 12h, and naturally cooling to room temperature after the reaction is finished;
step four: and opening the reaction kettle, taking out a product, washing the product by using absolute ethyl alcohol and deionized water in sequence, performing centrifugal separation, repeatedly washing for 5 times, and drying in a freeze dryer at the temperature of-60 ℃ and the vacuum degree of 25Pa to obtain black powder, namely the single-layer or few-layer tungsten disulfide nano material.
Example 5
The method comprises the following steps: adding 3.57g of tungsten hexachloride into 45mL of ethanol solution, and magnetically stirring until the tungsten hexachloride is completely dissolved to form a yellow clear solution A, wherein the stirring speed is 600r/min, and the stirring time is 60 min;
step two: adding 4.06g of thioacetamide into the solution A, and stirring to form a uniform mixed solution;
step three: transferring the solution to a 100mL polytetrafluoroethylene reaction kettle for homogeneous reaction, wherein the reaction temperature is 130 ℃, the reaction time is 18h, and naturally cooling to room temperature after the reaction is finished;
step four: and opening the reaction kettle, taking out a product, washing the product by using absolute ethyl alcohol and deionized water in sequence, performing centrifugal separation, repeatedly washing for 6 times, and drying in a freeze dryer at the temperature of-50 ℃ and the vacuum degree of 10Pa to obtain black powder, namely the single-layer or few-layer tungsten disulfide nano material.

Claims (5)

1. A preparation method of a single-layer or few-layer tungsten disulfide nano material is characterized by comprising the following steps:
the method comprises the following steps: adding 2.38-4.76 g of tungsten hexachloride into 30-60 mL of ethanol solution, and magnetically stirring until the tungsten hexachloride is completely dissolved to form a yellow clear solution A;
step two: adding 2.25-9.02 g of thioacetamide into the solution A, and uniformly stirring to form a mixed solution;
step three: transferring the mixed solution to a 100mL polytetrafluoroethylene reaction kettle for carrying out homogeneous reaction at the reaction temperature of 120-160 ℃ for 4-24 h, and naturally cooling to room temperature after the reaction is finished;
step four: and opening the reaction kettle, taking out the product, washing the product by using absolute ethyl alcohol and deionized water in sequence, centrifugally separating the product, and drying the product in a freeze dryer at the temperature of between 40 ℃ below zero and 70 ℃ below zero and the vacuum degree of 10 to 40Pa to obtain the single-layer or few-layer tungsten disulfide nano material.
2. The method for preparing single-layer or few-layer tungsten disulfide nano material according to claim 1, characterized in that: the concentration of the tungsten hexachloride in the step is 0.2 mol/L.
3. The method for preparing single-layer or few-layer tungsten disulfide nano material according to claim 1, characterized in that: in the first step, the magnetic stirring speed is 300-800 r/min, and the stirring time is 15-60 min.
4. The method for preparing single-layer or few-layer tungsten disulfide nano material according to claim 1, characterized in that: the molar ratio of thioacetamide to tungsten hexachloride added in the second step is 5-10: 1.
5. the method for preparing single-layer or few-layer tungsten disulfide nano material according to claim 1, characterized in that: and step four, repeatedly washing the mixture for 4-6 times by adopting absolute ethyl alcohol and deionized water.
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