CN112250044A - Preparation method of molybdenum diselenide submicron spheres - Google Patents
Preparation method of molybdenum diselenide submicron spheres Download PDFInfo
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- CN112250044A CN112250044A CN202011107993.4A CN202011107993A CN112250044A CN 112250044 A CN112250044 A CN 112250044A CN 202011107993 A CN202011107993 A CN 202011107993A CN 112250044 A CN112250044 A CN 112250044A
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- molybdenum diselenide
- molybdenum
- submicron
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- diselenide
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B19/00—Selenium; Tellurium; Compounds thereof
- C01B19/04—Binary compounds including binary selenium-tellurium compounds
Abstract
A preparation method of molybdenum diselenide submicron sphere material comprises the steps of dissolving ammonium molybdate tetrahydrate and potassium selenocyanate in water and ethylene glycol, adding polyvinylpyrrolidone serving as a reaction activator, putting the mixture into a high-pressure reaction kettle for solvothermal reaction, and stacking and polymerizing molybdenum diselenide nanosheets under thermodynamic stability and hydrogen bond interaction to form three-dimensional molybdenum diselenide layer submicron spheres. The product prepared by the method has good dispersibility, uniform particle size, low toxicity in the synthetic process, easy operation, low cost of experimental equipment and easy reappearance of experimental results. The molybdenum diselenide nano material synthesized by the method has excellent optical, electrochemical, catalytic and other properties, and can be widely applied to the fields of all-optical switches, photocatalysis, energy storage materials and the like.
Description
Technical Field
The invention relates to the field of nano materials, in particular to a preparation method of molybdenum diselenide submicron spheres.
Background
A transition metal dichalcogenide of the formula MX2The material has a unique sandwich-type atomic layer structure, the single-layer interaction is compact, and the layer-to-layer weak van der Waals force interaction is one of typical representatives of two-dimensional materials. Molybdenum diselenide belongs to a transition metal dichalcogenide, has a band gap of 1-2eV, and is widely applied to the fields of photocatalysis, electrochemistry, photoelectronic devices and the like due to the unique structure and performance of a thin atomic layer.
Researchers have found that molybdenum diselenide can produce different structures such as molybdenum diselenide nanowires, nanosheets, nanoflowers, nanorods and the like by self-assembly. Compared with other appearances, the three-dimensional molybdenum diselenide hierarchical submicron spheres serving as a novel material have large specific surface area and can provide larger photon absorption cross section, the whole submicron spheres are polymerized and accumulated by compact molybdenum diselenide nano sheets, and the self charge conduction efficiency is obviously improved by a developed carrier transmission channel inside. Meanwhile, the ultrathin nano sheet-shaped structures at the edges and folds of the composite material can provide a large number of reaction active sites and growth anchor points required by material compounding, can be combined with other materials to form a charge transfer channel, and improve the overall electron mobility of the composite material, so that the application and research values of the molybdenum diselenide submicron sphere material can be further expanded.
However, few methods for preparing spherical molybdenum diselenide are available, some methods adopt a template method, but have high cost, complex process and large particle size of the synthesized molybdenum diselenide microspheres, uneven dispersion and serious agglomeration phenomenon, some methods adopt toxic hydrazine hydrate as a reducing agent or use an organic solvent, which causes environmental pollution or harm to human health, and the improvement of performance and large-scale application of the method are limited.
Disclosure of Invention
The invention aims to provide a simple synthetic one-step solvothermal method, which is used for preparing molybdenum diselenide submicron spheres with uniform particle size and uniform dispersion in low-toxicity water and ethylene glycol, has excellent photoelectric properties, and can be widely applied to the fields of ultrafast photonics, photocatalysis, electrochemical materials and the like.
The above purpose is realized by the following technical scheme: the molybdenum source and the selenium source dissolved in water and glycol are fully mixed by ultrasonic stirring, and the molybdenum diselenide submicron spheres with good appearance are prepared in one step in a high-pressure reaction kettle by a solvothermal method after a reaction active agent is added. The specific steps of the scheme are as follows:
(1) ammonium molybdate tetrahydrate ((NH)4)6Mo7O24·4H2O) and potassium selenocyanate (NCSeCH)2COOK) powder was dissolved in 40ml of a mixed solution of water and ethylene glycol;
(2) adding a reaction activator polyvinylpyrrolidone (PVP) into the mixed solution, and stirring by ultrasonic and magnetic force to fully dissolve the mixed solution;
(3) transferring the mixed solution into a 50ml polytetrafluoroethylene inner lining, putting the inner lining into a stainless steel high-pressure reaction kettle, and carrying out high-temperature reaction in a vacuum drying oven;
(4) and after the reaction is finished, taking the reaction kettle out, naturally cooling to room temperature, centrifuging, collecting a black product, cleaning for 3 times by using deionized water and absolute ethyl alcohol to remove impurities, and drying in a vacuum drying oven to obtain a powder sample.
The content of the ammonium molybdate tetrahydrate in the step (1) is 0.014-0.286 mmol in water and ethylene glycol, the content of the potassium selenocyanate in the water and the ethylene glycol is 0.2-4 mmol, and the water is deionized water or ultrapure water.
The molar ratio of the molybdenum source to the selenium source in the step (1) is 1: 14.
The volume ratio of the water to the glycol in the step (1) is 1: 1.
The addition amount of the reactive agent in the step (2) is 0.02-0.4 g.
And (3) the time of ultrasonic and magnetic stirring in the step (2) is 15-60 min.
The high temperature in the step (3) is 190-230 ℃, the reaction time is 22-26 h, and the volume ratio of the volume of the added mixed solution to the volume of the polytetrafluoroethylene lining is about 80%.
And (4) drying the centrifugal machine in the step (4) for 6-12 hours at the temperature of 50-60 ℃ in a vacuum drying oven at the rotating speed of 8000-12000 r/min for 5-10 min to obtain the molybdenum diselenide submicron spheres.
Compared with the prior art, the invention has the technical effects that:
(1) the synthesized molybdenum diselenide submicron spheres have uniform particle size and good dispersibility, the submicron spheres have obvious outlines, and are not adhered and agglomerated.
(2) The method adopts a one-step solvothermal method, is simple and easy to synthesize, adopts water and glycol as solvents and glycol as reducing agents, and has the advantages of low toxicity and easy operation in experiments, low equipment cost required by the experiments and easy reappearance of experimental results.
(3) Particularly, the size of the prepared molybdenum diselenide submicron spheres is about 500nm, and the size of the molybdenum diselenide submicron spheres can be further changed by changing the concentration of reactants and the reaction time, so that the hierarchical submicron spheres with adjustable size and controllable range can be obtained.
(4) In the experiment, a two-dimensional material molybdenum diselenide nanosheet is accumulated and polymerized to form a three-dimensional hierarchical submicron sphere in a self-assembly mode, the specific surface area of the material is greatly improved, the carrier migration between the internal molybdenum diselenide ultrathin nanosheets is promoted, a composite material based on molybdenum diselenide can be synthesized through reactive sites at the edge and the folds of the submicron sphere, and the composite material is widely applied to the research fields of electrode materials, photocatalysis, super capacitors and the like.
Detailed Description
For better understanding of the present invention, the technical solution of the present invention will be described in detail below by using examples, but the scope of the present invention to be claimed is not limited to the following examples. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Example 1
Dissolving 0.071mmol of ammonium molybdate tetrahydrate in 20ml of water by ultrasonic stirring, dissolving 1.0mmol of potassium selenocyanate in 20ml of ethylene glycol by ultrasonic stirring, adding 0.10g of polyvinylpyrrolidone after the solutions are uniformly mixed, fully and ultrasonically stirring until the solutions are completely dissolved, then adding the mixed solution into a 50ml of polytetrafluoroethylene liner, putting the liner into a high-pressure reaction kettle, and reacting at the high temperature of 220 ℃ for 22 hours in a vacuum drying oven at constant temperature. And after the reaction is finished, collecting the product through centrifugal sedimentation at the rotating speed of 12000r/min for 10min, then washing the product for 3 times by using deionized water and absolute ethyl alcohol respectively to remove impurities, and drying the product in a vacuum drying oven at the temperature of 60 ℃ for 8 hours in vacuum to obtain the molybdenum diselenide submicron sphere powder sample.
Example 2
Dissolving 0.143mmol ammonium molybdate tetrahydrate in 20ml water by ultrasonic stirring, dissolving 2.0mmol potassium selenocyanate in 20ml ethylene glycol by ultrasonic stirring, adding 0.30g polyvinylpyrrolidone after the solution is uniformly mixed, fully and ultrasonically stirring until the solution is completely dissolved, then adding the mixed solution into 50ml polytetrafluoroethylene lining, putting the lining into a high-pressure reaction kettle, and reacting for 26 hours at a constant temperature of 190 ℃ in a vacuum drying oven. And after the reaction is finished, collecting the product by centrifugal sedimentation at the rotating speed of 10000r/min for 10min, then washing the product for 3 times respectively by using deionized water and absolute ethyl alcohol to remove impurities, and drying the product in a vacuum drying oven at the temperature of 50 ℃ for 8 hours to obtain the molybdenum diselenide submicron sphere powder sample.
Example 3
Dissolving 0.286mmol of ammonium molybdate tetrahydrate in 20ml of water by ultrasonic stirring, dissolving 4.0mmol of potassium selenocyanate in 20ml of ethylene glycol by ultrasonic stirring, adding 0.40g of polyvinylpyrrolidone after the solutions are uniformly mixed, fully and ultrasonically stirring until the solutions are completely dissolved, then adding the mixed solution into a 50ml of polytetrafluoroethylene liner, putting the liner into a high-pressure reaction kettle, and reacting for 22 hours at a constant temperature of 200 ℃ in a vacuum drying oven. And after the reaction is finished, collecting the product by centrifugal sedimentation at the rotating speed of 8000r/min for 10min, then washing the product for 3 times respectively by using deionized water and absolute ethyl alcohol to remove impurities, and carrying out vacuum drying in a vacuum drying oven at the temperature of 60 ℃ for 12h to obtain the molybdenum diselenide submicron sphere powder sample.
Example 4
Dissolving 0.036mmol of ammonium molybdate tetrahydrate in 20ml of water by ultrasonic stirring, dissolving 0.5mmol of potassium selenocyanate in 20ml of ethylene glycol by ultrasonic stirring, adding 0.04g of polyvinylpyrrolidone after the solutions are uniformly mixed, fully and ultrasonically stirring until the solutions are completely dissolved, then adding the mixed solution into a 50ml of polytetrafluoroethylene liner, putting the liner into a high-pressure reaction kettle, and carrying out constant-temperature reaction at the high temperature of 200 ℃ in a vacuum drying oven for 25 hours. And after the reaction is finished, collecting the product through centrifugal sedimentation at the rotating speed of 10000r/min for 8min, then washing the product for 3 times respectively by using deionized water and absolute ethyl alcohol to remove impurities, and drying the product in a vacuum drying oven at the temperature of 50 ℃ for 8 hours to obtain the molybdenum diselenide submicron sphere powder sample.
Example 5
Dissolving 0.036mmol of ammonium molybdate tetrahydrate in 20ml of water by ultrasonic stirring, dissolving 0.5mmol of potassium selenocyanate in 20ml of ethylene glycol by ultrasonic stirring, adding 0.25g of polyvinylpyrrolidone after the solutions are uniformly mixed, fully and ultrasonically stirring until the solutions are completely dissolved, then adding the mixed solution into a 50ml of polytetrafluoroethylene liner, putting the liner into a high-pressure reaction kettle, and reacting at the constant temperature of 200 ℃ for 24 hours in a vacuum drying oven. And after the reaction is finished, collecting the product through centrifugal sedimentation at the rotating speed of 9000r/min for 10min, then washing the product for 3 times respectively by using deionized water and absolute ethyl alcohol to remove impurities, and performing vacuum drying in a vacuum drying oven at the temperature of 50 ℃ for 8h to obtain the molybdenum diselenide submicron sphere powder sample.
Example 6
Dissolving 0.071mmol of ammonium molybdate tetrahydrate in 20ml of water by ultrasonic stirring, dissolving 1.0mmol of potassium selenocyanate in 20ml of ethylene glycol by ultrasonic stirring, adding 0.12g of polyvinylpyrrolidone after the solutions are uniformly mixed, fully and ultrasonically stirring until the solutions are completely dissolved, then adding the mixed solution into a 50ml of polytetrafluoroethylene liner, putting the liner into a high-pressure reaction kettle, and reacting at a constant temperature of 190 ℃ for 24 hours in a vacuum drying oven. And after the reaction is finished, collecting the product by centrifugal sedimentation at the rotating speed of 11000r/min for 10min, then respectively cleaning the product for 3 times by using deionized water and absolute ethyl alcohol to remove impurities, and carrying out vacuum drying in a vacuum drying oven at the temperature of 60 ℃ for 10h to obtain the molybdenum diselenide submicron sphere powder sample.
Claims (9)
1. A preparation method of molybdenum diselenide submicron sphere material is characterized in that molybdenum source and selenium source dissolved in 40ml of water and glycol are fully mixed, polyvinylpyrrolidone used as a reaction activator is added and then is put into a high-pressure reaction kettle for solvothermal reaction, and molybdenum diselenide nanosheets are stacked and polymerized under thermodynamic stability and hydrogen bond interaction to form three-dimensional molybdenum diselenide layer submicron spheres.
2. The method as set forth in claim 1, wherein the molybdenum source is ammonium molybdate tetrahydrate in an amount of 0.014 to 0.286mmol in water and ethylene glycol.
3. The method of claim 1, wherein the selenium source is potassium selenocyanate, and the content of the selenium source in water and ethylene glycol is 0.2-4 mmol.
4. The method of claim 1, wherein the molar ratio of the molybdenum source to the selenium source is 1: 14.
5. The method as set forth in claim 1, wherein the volume ratio of water to ethylene glycol is 1: 1.
6. The method according to claim 1, wherein the polyvinylpyrrolidone is added in an amount of 0.02 to 0.4 g.
7. The method according to claim 1, wherein the temperature of the solvothermal reaction is 190 to 230 ℃ and the reaction time is 22 to 26 hours.
8. The molybdenum diselenide submicron spheres prepared by the method of any one of the preceding claims, wherein the molybdenum diselenide submicron spheres have good dispersibility, the size distribution is 200-1200 nm, the average size is about 500nm, the three-dimensional molybdenum diselenide hierarchical submicron spheres are formed by stacking and polymerizing molybdenum diselenide nanosheets, and the thickness of the molybdenum diselenide nanosheets is 1-10 nm.
9. Use of molybdenum diselenide submicrospheres according to any of the preceding claims for material synthesis or for the preparation of composite materials.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113759445A (en) * | 2021-07-26 | 2021-12-07 | 南开大学 | Processing of partially random microlens arrays |
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| US3574658A (en) * | 1967-12-22 | 1971-04-13 | Ball Brothers Res Corp | Dry-lubricated surface and method of producing such surfaces |
| CN104511290A (en) * | 2014-12-31 | 2015-04-15 | 中国地质大学（武汉） | Preparation method of visible-light-driven photocatalyst nano spherical MoSe2 material |
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- 2020-10-16 CN CN202011107993.4A patent/CN112250044A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3574658A (en) * | 1967-12-22 | 1971-04-13 | Ball Brothers Res Corp | Dry-lubricated surface and method of producing such surfaces |
| CN104511290A (en) * | 2014-12-31 | 2015-04-15 | 中国地质大学（武汉） | Preparation method of visible-light-driven photocatalyst nano spherical MoSe2 material |
Non-Patent Citations (2)
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| GANGSHUO LIU等: "Preparation and comparison of nonlinear optical properties of MoSe2 with different types of structures", 《OPTICAL MATERIALS》 * |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113759445A (en) * | 2021-07-26 | 2021-12-07 | 南开大学 | Processing of partially random microlens arrays |
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Application publication date: 20210122 |