CN109399722B - Preparation method of porous rod-like molybdenum dioxide/carbon composite material - Google Patents
Preparation method of porous rod-like molybdenum dioxide/carbon composite material Download PDFInfo
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- CN109399722B CN109399722B CN201811609841.7A CN201811609841A CN109399722B CN 109399722 B CN109399722 B CN 109399722B CN 201811609841 A CN201811609841 A CN 201811609841A CN 109399722 B CN109399722 B CN 109399722B
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Abstract
The invention discloses a preparation method of a porous rod-shaped molybdenum dioxide/carbon composite material, which comprises the following steps of firstly, preparing ammonium molybdate tetrahydrate aqueous solution; then adding polyvinyl alcohol into ammonium molybdate tetrahydrate aqueous solution, stirring at normal temperature, and then heating and stirring to obtain mixed solution; after the mixed solution is cooled to room temperature, freeze-drying to obtain a freeze-dried product; and finally, calcining the freeze-dried product, and obtaining the porous rod-like molybdenum dioxide/carbon composite material after calcining. The method has the advantages of simple preparation process, good repeatability and low cost, and can prepare the porous rod-like molybdenum dioxide/carbon composite material with large specific surface area.
Description
Technical Field
The invention belongs to the field of inorganic material preparation, and particularly relates to a preparation method of a porous rod-like molybdenum dioxide/carbon composite material.
Background
Molybdenum dioxide is a transition metal oxide with low resistivity, high melting point, good thermal and chemical stability. Due to the unique structure and property, the molybdenum dioxide has wide application prospect in the fields of photocatalysis, supercapacitors, lithium ion batteries and the like. Aiming at the defects that molybdenum dioxide has few active sites and is easy to agglomerate and the like, the preparation of the composite material based on molybdenum dioxide is called as a research hotspot. The Chinese invention patent CN106492820B discloses a preparation method of molybdenum dioxide loaded cobalt oxide particles with three-dimensional macroporous structures; chinese patent 102795667B discloses a preparation method of a carbon-coated nano molybdenum dioxide material; the Chinese invention patent 106219616A discloses a molybdenum dioxide/nickel cobaltate hierarchical hybrid nanostructure array and a preparation method thereof, and the preparation method of the invention has the problem of relatively complex process.
Disclosure of Invention
The invention aims to provide a preparation method of a porous rod-shaped molybdenum dioxide/carbon composite material, which overcomes the defects in the prior art, has simple preparation process, good repeatability and low cost, and can prepare the porous rod-shaped molybdenum dioxide/carbon composite material with large specific surface area.
In order to achieve the purpose, the invention adopts the following technical scheme:
a preparation method of a porous rod-shaped molybdenum dioxide/carbon composite material comprises the following steps:
the method comprises the following steps: preparing ammonium molybdate tetrahydrate aqueous solution;
step two: adding polyvinyl alcohol into ammonium molybdate tetrahydrate aqueous solution, stirring at normal temperature, and then heating and stirring to obtain mixed solution;
step three: after the mixed solution is cooled to room temperature, freeze-drying to obtain a freeze-dried product;
step four: and calcining the freeze-dried product, and calcining to obtain the porous rod-like molybdenum dioxide/carbon composite material.
Further, the concentration of the ammonium molybdate tetrahydrate aqueous solution in the first step is 0.04 mol/L.
Further, in the second step, 5-25 g of polyvinyl alcohol is added into every 200mL of ammonium molybdate tetrahydrate aqueous solution.
Further, the stirring time at normal temperature in the second step is 0.5 h.
Further, the temperature of the heating and stirring in the second step is 85 ℃ and the time is 1 h.
Further, the temperature of freeze drying in the third step is-40 ℃ and the time is 48 h.
Further, the calcination in the fourth step is specifically: putting the freeze-dried product into a tube furnace, calcining for 2h at 700 ℃ under inert atmosphere, and raising the temperature at 3 ℃/min.
Compared with the prior art, the invention has the following beneficial technical effects:
the preparation method of the porous rod-shaped molybdenum dioxide/carbon composite material provided by the invention comprises the step of calcining the porous rod-shaped molybdenum dioxide/carbon composite material in an argon atmosphere by freeze drying under the auxiliary action of polyvinyl alcohol. The method is simple to operate and low in cost, and the specific surface area is effectively improved due to the porous rod-like structure of the molybdenum dioxide/carbon composite material, so that more active sites can be provided, and the molybdenum dioxide/carbon composite material has potential application value in the fields of catalysis and energy storage.
Drawings
FIG. 1 is an SEM image of a molybdenum dioxide/carbon composite of example 2 of the present invention, wherein (a) is an enlargement of 1K and (b) is an enlargement of 10K;
FIG. 2 is an XRD pattern of a molybdenum dioxide/carbon composite material according to example 2 of the present invention;
FIG. 3 is a Raman diagram of a molybdenum dioxide/carbon composite material according to example 2 of the present invention.
Detailed Description
Embodiments of the invention are described in further detail below:
a preparation method of a porous rod-shaped molybdenum dioxide/carbon composite material comprises the following steps:
1) 200mL of 0.04mol/L ammonium molybdate tetrahydrate aqueous solution is prepared.
2) 5-25 g of polyvinyl alcohol (1788 type) is added into the solution, stirred for 0.5h at normal temperature and then stirred for 1h at 85 ℃.
3) After the mixed solution was cooled, it was freeze-dried at-40 ℃ for 48 hours.
4) And putting the freeze-dried product into a tubular furnace, calcining for 2h at the temperature of 700 ℃ in the atmosphere, wherein the heating rate is 3 ℃/min, and obtaining the porous rod-like molybdenum dioxide/carbon composite material after calcining and sintering.
The present invention is described in further detail below with reference to examples:
example 1
1) In the first step, 200mL of 0.04mol/L ammonium molybdate tetrahydrate aqueous solution is prepared.
2) In the second step, 5g of polyvinyl alcohol (1788 type) was added to the above solution, stirred at room temperature for 0.5h, and then stirred at 85 ℃ for 1 h.
3) And thirdly, after the mixed solution is cooled, freezing and drying the mixed solution for 48 hours at the temperature of minus 40 ℃.
4) Fourthly, putting the freeze-dried product into a tube furnace, calcining for 2h at the temperature of 700 ℃ in the atmosphere, wherein the heating rate is 3 ℃/min, and obtaining the porous rod-shaped molybdenum dioxide/carbon composite material after calcining and sintering.
Example 2
1) In the first step, 200mL of 0.04mol/L ammonium molybdate tetrahydrate aqueous solution is prepared.
2) In the second step, 20g of polyvinyl alcohol (1788 type) was added to the above solution, stirred at room temperature for 0.5h, and then stirred at 85 ℃ for 1 h.
3) And thirdly, after the mixed solution is cooled, freezing and drying the mixed solution for 48 hours at the temperature of minus 40 ℃.
4) Fourthly, putting the freeze-dried product into a tube furnace, calcining for 2h at the temperature of 700 ℃ in the atmosphere, wherein the heating rate is 3 ℃/min, and obtaining the porous rod-shaped molybdenum dioxide/carbon composite material after calcining and sintering.
Example 3
1) In the first step, 200mL of 0.04mol/L ammonium molybdate tetrahydrate aqueous solution is prepared.
2) In the second step, 25g of polyvinyl alcohol (1788 type) was added to the above solution, stirred at room temperature for 0.5h, and then stirred at 85 ℃ for 1 h.
3) And thirdly, after the mixed solution is cooled, freezing and drying the mixed solution for 48 hours at the temperature of minus 40 ℃.
4) Fourthly, putting the freeze-dried product into a tube furnace, calcining for 2h at the temperature of 700 ℃ in the atmosphere, wherein the heating rate is 3 ℃/min, and obtaining the porous rod-shaped molybdenum dioxide/carbon composite material after calcining and sintering.
FIG. 1 is an SEM image of a molybdenum dioxide/carbon composite of example 2. The figure shows that the prepared molybdenum dioxide/carbon composite material is a micron-sized short rod, and the interior and the surface of the short rod have rich pore structures, so that the specific surface area and the electrochemical performance of the material are favorably improved.
Figure 2 is an XRD pattern of the molybdenum dioxide/carbon composite of example 2. The main diffraction peak in the figure is consistent with molybdenum dioxide (PDF #32-0671), and the peak shape is sharp, which indicates that the molybdenum dioxide in the molybdenum dioxide/carbon composite material has high crystallinity and purity.
FIG. 3 is a Raman plot of the molybdenum dioxide/carbon composite of example 2. It can be seen that, in addition to the characteristic peak of molybdenum dioxide, there is a distinct characteristic peak of carbon, indicating that the product is a composite of molybdenum dioxide and carbon.
Claims (1)
1. The preparation method of the porous rod-shaped molybdenum dioxide/carbon composite material is characterized by comprising the following steps of:
the method comprises the following steps: preparing an ammonium molybdate tetrahydrate aqueous solution, wherein the concentration of the ammonium molybdate tetrahydrate aqueous solution is 0.04 mol/L;
step two: adding polyvinyl alcohol into ammonium molybdate tetrahydrate aqueous solution, adding 5-25 g of polyvinyl alcohol into every 200mL of ammonium molybdate tetrahydrate aqueous solution, stirring at normal temperature for 0.5h, heating to 85 ℃, and stirring for 1h to obtain mixed solution;
step three: after the mixed solution is cooled to room temperature, freeze-drying to obtain a freeze-dried product, wherein the freeze-drying temperature is-40 ℃, and the time is 48 hours;
step four: and putting the freeze-dried product into a tubular furnace, calcining for 2h at 700 ℃ in an inert atmosphere, wherein the heating rate is 3 ℃/min, and obtaining the porous rod-like molybdenum dioxide/carbon composite material after calcining and sintering.
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| CN114232015A (en) * | 2022-01-10 | 2022-03-25 | 齐鲁工业大学 | Tubular MoO2Preparation and application of/C composite material |
| CN114743807B (en) * | 2022-05-19 | 2024-03-19 | 江苏大学 | Internally and externally generated MoO 2 Preparation method of three-dimensional carbon composite material |
| CN115000370A (en) * | 2022-06-02 | 2022-09-02 | 烟台大学 | Molybdenum dioxide confinement growth and modification three-dimensional porous carbon composite electrode material and preparation method thereof |
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| CN102623687A (en) * | 2012-04-09 | 2012-08-01 | 华中科技大学 | Preparation method for high-capacity molybdenum dioxide anode material and application of high-capacity molybdenum dioxide anode material |
| CN103288136A (en) * | 2012-02-27 | 2013-09-11 | 新疆教育学院 | Hydrothermal synthesis method of shape-controllable molybdenum dioxide submicrocrystals |
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| CN107394163A (en) * | 2017-07-25 | 2017-11-24 | 陕西科技大学 | A kind of copper molybdenum dioxide carbon composite of hollow core shell structure and its preparation method and application |
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Patent Citations (4)
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| CN103288136A (en) * | 2012-02-27 | 2013-09-11 | 新疆教育学院 | Hydrothermal synthesis method of shape-controllable molybdenum dioxide submicrocrystals |
| CN102623687A (en) * | 2012-04-09 | 2012-08-01 | 华中科技大学 | Preparation method for high-capacity molybdenum dioxide anode material and application of high-capacity molybdenum dioxide anode material |
| CN106299259A (en) * | 2015-05-18 | 2017-01-04 | 韦升鸿 | The preparation method of a kind of molybdenum dioxide/carbon nano-particle and in the application of lithium ion battery |
| CN107394163A (en) * | 2017-07-25 | 2017-11-24 | 陕西科技大学 | A kind of copper molybdenum dioxide carbon composite of hollow core shell structure and its preparation method and application |
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