CN116135311A - Nanometer material based on molybdenum disulfide network structure and preparation method and application thereof - Google Patents

Nanometer material based on molybdenum disulfide network structure and preparation method and application thereof Download PDF

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CN116135311A
CN116135311A CN202310424628.3A CN202310424628A CN116135311A CN 116135311 A CN116135311 A CN 116135311A CN 202310424628 A CN202310424628 A CN 202310424628A CN 116135311 A CN116135311 A CN 116135311A
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molybdenum disulfide
network structure
aqueous solution
nano material
preparing
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CN116135311B (en
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杨文府
汪雯雯
张文凯
郭绍辉
郝晓阳
马玉龙
郭祺
李佳芳
姜姝芬
殷亮
冯婧
张丽芳
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Shanxi Coal Geological And Geophysical Survey And Mapping Institute Co ltd
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Shanxi Coal Geological And Geophysical Survey And Mapping Institute Co ltd
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    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D53/00Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34Chemical or biological purification of waste gases
    • B01D53/74General processes for purification of waste gases; Apparatus or devices specially adapted therefor
    • B01D53/86Catalytic processes
    • B01D53/8668Removing organic compounds not provided for in B01D53/8603 - B01D53/8665
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D53/00Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/007Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by irradiation
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D53/00Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/02Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/02Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • B01J35/39
    • B01J35/51
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D2257/00Components to be removed
    • B01D2257/70Organic compounds not provided for in groups B01D2257/00 - B01D2257/602
    • B01D2257/704Solvents not covered by groups B01D2257/702 - B01D2257/7027
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D2259/00Type of treatment
    • B01D2259/80Employing electric, magnetic, electromagnetic or wave energy, or particle radiation
    • B01D2259/802Visible light

Abstract

The invention provides a nano material based on a molybdenum disulfide network structure and a preparation method thereof, wherein the method comprises the following steps: mixing an aqueous solution of cysteine with an aqueous solution of anhydrous sodium molybdate, and then performing ultrasonic treatment to obtain a molybdenum disulfide precursor solution; carrying out hydrothermal reaction on the molybdenum disulfide precursor solution, and washing and centrifuging after the reaction is finished to obtain a molybdenum disulfide nanosphere material; adding the molybdenum disulfide nanosphere material into toluene solution, carrying out centrifugal cleaning after ultrasonic treatment, and obtaining the nanomaterial with a molybdenum disulfide nanosphere network structure. The nano material based on the molybdenum disulfide network structure is used for removing formaldehyde. According to the invention, molybdenum disulfide is a novel two-dimensional material, the absorption range is from an ultraviolet light region to a visible light region, and good catalytic active sites are arranged at the edge of the molybdenum disulfide, so that formaldehyde can be effectively adsorbed and degraded.

Description

Nanometer material based on molybdenum disulfide network structure and preparation method and application thereof
Technical Field
The invention belongs to the technical field of catalysis, and particularly relates to a nano material based on a molybdenum disulfide network structure, and a preparation method and application thereof.
Background
The formaldehyde problem is currently of great concern in the market due to the use of various finishing materials. The thought of photocatalyst formaldehyde removal is proposed. However, the photocatalyst for removing formaldehyde at present mainly uses nano titanium dioxide as a raw material. These materials are concentrated mainly in the ultraviolet region for the light absorption range, resulting in an insufficient formaldehyde removal effect. Aiming at the problem, a nano material based on a molybdenum disulfide network structure and a preparation method thereof are provided.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a nano material based on a molybdenum disulfide network structure, a preparation method and application thereof, wherein the method utilizes a hydrothermal method to construct molybdenum disulfide nanospheres; the molybdenum disulfide has light absorption in the visible light region, so that the problem of limitation of the light absorption range of the titanium dioxide-based photocatalyst can be effectively solved. Due to the good catalytic active site at the edge of the molybdenum disulfide, formaldehyde degradation can be effectively realized; in addition, the molybdenum disulfide balls are mutually entangled after being treated, so that a huge network structure can be formed, and formaldehyde adsorption is facilitated.
In order to solve the technical problems, the invention adopts the following technical scheme: a preparation method of a nano material based on a molybdenum disulfide network structure comprises the following steps:
s1, preparing a molybdenum disulfide precursor solution: dissolving cysteine in deionized water to obtain cysteine aqueous solution; dissolving anhydrous sodium molybdate in deionized water to obtain an anhydrous sodium molybdate aqueous solution; mixing the cysteine aqueous solution and the anhydrous sodium molybdate aqueous solution, and performing ultrasonic treatment to obtain a molybdenum disulfide precursor solution;
s2, preparing a molybdenum disulfide nanosphere material: carrying out hydrothermal reaction on the molybdenum disulfide precursor solution obtained in the step S1 at the temperature of 200 ℃ for 10-24 hours, and carrying out centrifugal cleaning after the hydrothermal reaction is finished to obtain a molybdenum disulfide nanosphere material;
s3, preparing a nano material: and (3) adding the molybdenum disulfide nanosphere material obtained in the step (S2) into toluene for ultrasonic treatment, and then performing centrifugal cleaning treatment to obtain a nanomaterial, wherein the nanomaterial is of a molybdenum disulfide nanosphere network structure.
Preferably, the concentration of the cysteine aqueous solution in S1 is 1-2%, and the concentration of the anhydrous sodium molybdate aqueous solution is 0.5-1%.
Preferably, the volume ratio of the cysteine aqueous solution to the anhydrous sodium molybdate aqueous solution in the S1 is 3:1.
Preferably, the time of the ultrasonic treatment in S1 is 2-4 hours.
Preferably, the dosage of the cysteine in the S1 is 1-2 g, and when the dosage of the anhydrous sodium molybdate is 0.5-1 g, the dosage of the toluene solution in the S3 is 10-30mL.
Preferably, the time of the ultrasonic treatment in S3 is 1-3h, and the frequency is 50KHz.
The application of the nano material based on the molybdenum disulfide network structure is also provided, and the nano material based on the molybdenum disulfide network structure is used for removing formaldehyde.
The nano material based on the molybdenum disulfide network structure is also provided, and the nano material based on the molybdenum disulfide network structure is prepared by the method.
Compared with the prior art, the invention has the following advantages:
compared with titanium dioxide photocatalyst, the molybdenum disulfide nanospheres provided by the invention have strong light absorption in a visible light region, and can realize formaldehyde degradation under visible light; on the other hand, the molybdenum disulfide nano ball net structure can effectively adsorb formaldehyde, and the active sites at the edge of the molybdenum disulfide nano ball net structure can be used as reaction centers for catalytic degradation, so that the formaldehyde removal efficiency is greatly improved. In addition, the photocatalyst is nontoxic to human body, does not cause environmental pollution, and has quick response, good durability, simple production process and low manufacturing cost.
The invention is described in further detail below with reference to the drawings and examples.
Drawings
FIG. 1 is a scanning electron micrograph (. Times.10 μm) of a nanomaterial produced in example 1 of the present invention,
FIG. 2 is a scanning electron micrograph (. Times.0.2 μm) of the nanomaterial produced in example 1 of the present invention,
FIG. 3 is a transmission electron micrograph (. Times.10 μm) of the nanomaterial made in example 1 of the present invention,
figure 4 (a) is a toluene chemical formula,
FIG. 4 (b) is toluene and MoS 2 A schematic diagram of the combination of nanospheres,
FIG. 5 is a graph showing the results of formaldehyde adsorption experiments performed on the nanomaterial prepared in example 1 of the present invention,
FIG. 6 is a graph showing the results of repeated formaldehyde adsorption experiments on the nanomaterial prepared in example 1 of the present invention.
Description of the embodiments
Example 1
The preparation method of the nano material based on the molybdenum disulfide network structure provided by the embodiment comprises the following steps:
s1, preparing a molybdenum disulfide precursor solution: 1.0g of cysteine was dissolved in 100mL of deionized water to obtain an aqueous solution of cysteine; dissolving 0.5g of anhydrous sodium molybdate in 100mL of deionized water to obtain an anhydrous sodium molybdate aqueous solution; mixing the cysteine aqueous solution and the anhydrous sodium molybdate aqueous solution according to the volume ratio of 3:1, and performing ultrasonic treatment for 2 hours to obtain a molybdenum disulfide precursor solution;
s2, preparing a molybdenum disulfide nanosphere material: carrying out hydrothermal reaction on the molybdenum disulfide precursor solution obtained in the step S1 at the temperature of 200 ℃ for 10 hours, and carrying out centrifugal cleaning after the hydrothermal reaction is finished to obtain a molybdenum disulfide nanosphere material;
s3, preparing a nano material: and (3) adding the molybdenum disulfide nanosphere material obtained in the step (S2) into 10mL of toluene solution for ultrasonic treatment for 1h, and then performing centrifugal cleaning treatment to obtain a nanomaterial, wherein the nanomaterial is of a molybdenum disulfide nanosphere network structure.
Toluene is an organic compound (chemical structural formula shown in figure 4 (a)) and has a chemical formula of C 7 H 8 Of the structural functional group methyl-CH 3 Easy to be combined with MoS 2 S in toluene is bonded, and C in benzene ring structure in toluene can be bonded with MoS 2 S in (a) is coordinately bound (shown in FIG. 4 (b)). Toluene can thus be used as MoS 2 The connectors between nanospheres are also an important part of the formation of the nanosphere network structure. The toluene is chosen here on the one hand for its structural function methyl-CH 3 And C in the benzene ring structure is easy to MoS 2 S in the ball grid array is coordinated and combined into a bond, so that a nano ball grid array structure is formed; on the other hand, toluene is relatively active and can be compared with MoS 2 The nanospheres are combined rapidly, the free energy of the whole reaction system is reduced, and the stability of a network structure is improved.
The scanning electron microscope diagram of the nano material prepared by the embodiment is shown in fig. 1, and it can be seen that the nanospheres are connected with each other to form a network structure; the MoS can be seen from the scanning electron microscope of FIG. 2 2 The nano materials are mutually combined; nano material transmission electron microscopeThe figure is shown in FIG. 3, two MoS can be seen in FIG. 3 2 The edges of the nanospheres are intertwined.
The formaldehyde adsorption experiment is carried out by using the nano material prepared in the embodiment, and the experimental process is as follows: 50mg of nanomaterial is taken for adsorption, and the result is shown in FIG. 5; as can be seen from FIG. 5, the initial concentration of formaldehyde is 2.0mg/m 3 The formaldehyde concentration is reduced to 0.02mg/m after 600s absorption 3
The formaldehyde adsorption experiment is subjected to cyclic test, a group of nano materials are taken for repeated test, the total cyclic time is 5 times, the results are shown in fig. 6, and the results of the 5 times of experiments are basically identical, so that the nano materials prepared by the embodiment can adsorb formaldehyde and can be recycled.
Example 2
The preparation method of the nano material based on the molybdenum disulfide network structure provided by the embodiment comprises the following steps:
s1, preparing a molybdenum disulfide precursor solution: 2.0g of cysteine is dissolved in 100mL of deionized water to obtain cysteine aqueous solution; 1g of anhydrous sodium molybdate is taken and dissolved in 100mL of deionized water to obtain an anhydrous sodium molybdate aqueous solution; mixing the cysteine aqueous solution and the anhydrous sodium molybdate aqueous solution according to the volume ratio of 3:1, and performing ultrasonic treatment for 4 hours to obtain a molybdenum disulfide precursor solution;
s2, preparing a molybdenum disulfide nanosphere material: carrying out hydrothermal reaction on the molybdenum disulfide precursor solution obtained in the step S1 at the temperature of 200 ℃ for 24 hours, and carrying out centrifugal cleaning after the hydrothermal reaction is finished to obtain a molybdenum disulfide nanosphere material;
s3, preparing a nano material: and (3) adding the molybdenum disulfide nanosphere material obtained in the step (S2) into 30mL of toluene solution for ultrasonic treatment for 3h, and then performing centrifugal cleaning treatment to obtain a nanomaterial, wherein the nanomaterial is of a molybdenum disulfide nanosphere network structure.
Through detection, the structure of the nano material prepared by the embodiment is a molybdenum disulfide nano ball net structure.
The formaldehyde adsorption experiment is carried out by using the nano material prepared in the embodiment, and the experimental result is as follows: the initial concentration of formaldehyde is 2.0mg/m 3 Adsorbing 50mg of nano material, and reducing formaldehyde concentration to 0.4mg/m after 600s of adsorption 3
Example 3
The preparation method of the nano material based on the molybdenum disulfide network structure provided by the embodiment comprises the following steps:
s1, preparing a molybdenum disulfide precursor solution: 1.5g of cysteine is dissolved in 100mL of deionized water to obtain cysteine aqueous solution; dissolving 0.7g of anhydrous sodium molybdate in 100mL of deionized water to obtain an anhydrous sodium molybdate aqueous solution; mixing the cysteine aqueous solution and the anhydrous sodium molybdate aqueous solution according to the volume ratio of 3:1, and performing ultrasonic treatment for 3 hours to obtain a molybdenum disulfide precursor solution;
s2, preparing a molybdenum disulfide nanosphere material: carrying out hydrothermal reaction on the molybdenum disulfide precursor solution obtained in the step S1 at the temperature of 200 ℃ for 14h, and carrying out centrifugal cleaning after the hydrothermal reaction is finished to obtain a molybdenum disulfide nanosphere material;
s3, preparing a nano material: and (3) adding the molybdenum disulfide nanosphere material obtained in the step (S2) into 15mL of toluene solution for ultrasonic treatment for 2 hours, and then performing centrifugal cleaning treatment to obtain a nanomaterial, wherein the nanomaterial is of a molybdenum disulfide nanosphere network structure.
Through detection, the structure of the nano material prepared by the embodiment is a molybdenum disulfide nano ball net structure.
The formaldehyde adsorption experiment is carried out by using the nano material prepared in the embodiment, and the experimental result is as follows: the initial concentration of formaldehyde is 2.0mg/m 3 Adsorbing 50mg of nano material, and reducing formaldehyde concentration to 0.1mg/m after 600s of adsorption 3
Example 4
The preparation method of the nano material based on the molybdenum disulfide network structure provided by the embodiment comprises the following steps:
s1, preparing a molybdenum disulfide precursor solution: 2.0g of cysteine is dissolved in 100mL of deionized water to obtain cysteine aqueous solution; dissolving 0.5g of anhydrous sodium molybdate in 100mL of deionized water to obtain an anhydrous sodium molybdate aqueous solution; mixing the cysteine aqueous solution and the anhydrous sodium molybdate aqueous solution according to the volume ratio of 3:1, and performing ultrasonic treatment for 3 hours to obtain a molybdenum disulfide precursor solution;
s2, preparing a molybdenum disulfide nanosphere material: carrying out hydrothermal reaction on the molybdenum disulfide precursor solution obtained in the step S1 at the temperature of 200 ℃ for 16 hours, and carrying out centrifugal cleaning after the hydrothermal reaction is finished to obtain a molybdenum disulfide nanosphere material;
s3, preparing a nano material: and (3) adding the molybdenum disulfide nanosphere material obtained in the step (S2) into 25mL of toluene solution for ultrasonic treatment for 1.5h, and then performing centrifugal cleaning treatment to obtain a nanomaterial, wherein the nanomaterial is of a molybdenum disulfide nanosphere network structure.
Through detection, the structure of the nano material prepared by the embodiment is a molybdenum disulfide nano ball net structure.
The nanometer material prepared in the embodiment is used for formaldehyde adsorption experiments, and the initial concentration of formaldehyde is 2.0mg/m 3 Adsorbing 50mg of nano material, and reducing formaldehyde concentration to 0.2mg/m after 600s of adsorption 3
The above description is only of the preferred embodiments of the present invention, and is not intended to limit the present invention. Any simple modification, variation and equivalent variation of the above embodiments according to the technical substance of the invention still fall within the scope of the technical solution of the invention.

Claims (8)

1. The preparation method of the nano material based on the molybdenum disulfide network structure is characterized by comprising the following steps of:
s1, preparing a molybdenum disulfide precursor solution: dissolving cysteine in deionized water to obtain cysteine aqueous solution; dissolving anhydrous sodium molybdate in deionized water to obtain an anhydrous sodium molybdate aqueous solution; mixing the cysteine aqueous solution and the anhydrous sodium molybdate aqueous solution, and performing ultrasonic treatment to obtain a molybdenum disulfide precursor solution;
s2, preparing a molybdenum disulfide nanosphere material: carrying out hydrothermal reaction on the molybdenum disulfide precursor solution obtained in the step S1 at the temperature of 200 ℃ for 10-24 hours, and carrying out centrifugal cleaning after the hydrothermal reaction is finished to obtain a molybdenum disulfide nanosphere material;
s3, preparing a nano material: and (3) adding the molybdenum disulfide nanosphere material obtained in the step (S2) into toluene for ultrasonic treatment, and then performing centrifugal cleaning treatment to obtain a nanomaterial, wherein the nanomaterial is of a molybdenum disulfide nanosphere network structure.
2. The method for preparing the nano material based on the molybdenum disulfide network structure according to claim 1, wherein the concentration of the cysteine aqueous solution in S1 is 1-2%, and the concentration of the anhydrous sodium molybdate aqueous solution is 0.5-1%.
3. The method for preparing the nano material based on the molybdenum disulfide network structure according to claim 1, wherein the volume ratio of the cysteine aqueous solution to the anhydrous sodium molybdate aqueous solution in the S1 is 3:1.
4. The method for preparing the nano material based on the molybdenum disulfide network structure according to claim 1, wherein the time of the ultrasonic treatment in the step S1 is 2-4h.
5. The method for preparing the nano material based on the molybdenum disulfide network structure according to claim 3, wherein the dosage of the cysteine in S1 is 1-2 g, and when the dosage of the anhydrous sodium molybdate is 0.5-1 g, the dosage of the toluene in S3 is 10-30mL.
6. The method for preparing the nano material based on the molybdenum disulfide network structure according to claim 1, wherein the ultrasonic treatment in the step S3 is carried out for 1-3h at a frequency of 50KHz.
7. A nanomaterial based on molybdenum disulfide network structure, characterized in that the nanomaterial based on molybdenum disulfide network structure prepared by the method of any one of claims 1-6.
8. The use of a nanomaterial based on a molybdenum disulfide network as claimed in claim 7 for removing formaldehyde.
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