CN113184912B - Method for preparing hierarchical tungsten trioxide with assistance of microwaves - Google Patents
Method for preparing hierarchical tungsten trioxide with assistance of microwaves Download PDFInfo
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Abstract
The invention provides a method for preparing hierarchical tungsten trioxide by microwave assistance, which comprises the steps of obtaining a tungsten trioxide precursor by a microwave-assisted precipitation method, and calcining the tungsten trioxide precursor; in the microwave-assisted precipitation method, tungsten hexachloride and oxalic acid are dispersed in an organic solvent for reaction. The invention provides a microwave-assisted method for preparing hierarchical tungsten trioxide, which is characterized in that a tungsten trioxide precursor is obtained by adopting a microwave-assisted precipitation method and then calcined, so that the hierarchical tungsten trioxide can be conveniently and quickly obtained, and the method has low equipment requirement and high repeatability and is easier to popularize compared with other methods.
Description
Technical Field
The invention relates to the technical field of preparation of nano materials, in particular to a method for preparing hierarchical tungsten trioxide by microwave assistance.
Background
Tungsten trioxide (WO) 3 ) The N-type semiconductor metal oxide has the forbidden band width of 2.4-2.8 eV, can absorb most visible light, has higher solar spectrum utilization rate, is concerned about electrochromism and photochromism due to abundant and easily prepared raw materials, light corrosion resistance, good light stability and excellent electrochromism and has great application prospect in the fields of sensing devices, photoelectric energy storage materials, water pollution treatment and the like.
Compared with a block material, the nano tungsten trioxide material has some unique properties, such as excellent photocatalytic performance, excellent gas-sensitive response and the like. Therefore, the synthesis of nano tungsten trioxide materials of different morphologies, such as nanoparticles, nanotubes, nanowires, nanorods, nanosheets, nanoplates, hollow spheres and three-dimensional hierarchical structures, has been widely studied.
At present, the preparation methods of the nano tungsten trioxide material mainly comprise a sol-gel method, a hydrothermal method, a solvothermal method, a template method and the like. The whole preparation process of the sol-gel method needs longer time, which usually needs several days or weeks; the template method is complicated in post-treatment process, and template impurities may remain in the product; the hydrothermal method and the solvothermal method can be used for preparing nano tungsten trioxide materials with various shapes, but the whole preparation process is carried out under the conditions of high temperature and high pressure, and the requirement on equipment is high.
Disclosure of Invention
Aiming at the defects in the prior art, the invention provides a method for preparing hierarchical tungsten trioxide by microwave assistance, which has the advantages of simple operation, short reaction time, low equipment requirement and high repeatability.
The invention adopts the following technical scheme:
the invention provides a method for preparing tungsten trioxide with a hierarchical structure by microwave assistance, which comprises the steps of obtaining a tungsten trioxide precursor by a microwave-assisted precipitation method, and calcining the tungsten trioxide precursor;
in the microwave-assisted precipitation method, tungsten hexachloride and oxalic acid are dispersed in an organic solvent for reaction.
The research of the invention finds that the tungsten trioxide precursor is obtained by adopting a microwave-assisted precipitation method and then calcined, so that the tungsten trioxide with the hierarchical structure can be conveniently and quickly obtained, and the method has low requirement on equipment and high repeatability. Wherein, the microwave-assisted precipitation method needs to adopt tungsten hexachloride as a tungsten source to react with oxalic acid dispersed in an organic solvent, so as to obtain a relatively ideal product.
Preferably, the organic solvent is ethanol.
Preferably, the concentration of the tungsten hexachloride is 0.005-0.025mol/L, preferably 0.01mol/L, and the concentration of the shape control agent is 0.05-0.20mol/L, preferably 0.1mol/L.
Further, the microwave-assisted precipitation method is characterized in that heating is performed at a constant microwave power.
Preferably, the microwave power is 300-600W, and the heating time is 30-60 min.
Further, the temperature for calcining the tungsten trioxide precursor is 400-550 ℃, preferably 500 ℃, and the temperature is kept for 1-6 h.
In a specific embodiment of the invention, the method for preparing hierarchical tungsten trioxide by microwave assistance specifically comprises the following steps:
s1, dispersing tungsten hexachloride and oxalic acid in an organic solvent, and stirring in an air atmosphere to obtain a precursor solution;
s2, performing microwave heating on the precursor solution at normal temperature and normal pressure, wherein the reactor is externally connected with a condensation reflux device, the microwave power is 300-600W, and the heating time is 30-60 min;
s3, standing and cooling to room temperature after the reaction is finished, carrying out centrifugal separation on a reaction product, repeatedly washing and centrifuging the obtained solid substance by using an organic solvent, and drying for later use;
and S4, calcining the dried product, setting the temperature to be 500 ℃, preserving the heat for 1-6 h, taking out the product, placing the product in the air, and cooling the product to the room temperature to obtain the catalyst.
The invention also provides the tungsten trioxide with the hierarchical structure prepared by any one of the preparation methods.
The invention provides a microwave-assisted method for preparing hierarchical tungsten trioxide, which is characterized in that a tungsten trioxide precursor is obtained by adopting a microwave-assisted precipitation method and then calcined, so that the hierarchical tungsten trioxide can be conveniently and quickly obtained, and the method has low equipment requirement and high repeatability and is easier to popularize compared with other methods.
Drawings
FIG. 1 is an SEM photograph (magnification of 50000 times) of a hierarchical tungsten trioxide prepared in example 1 of the present invention;
FIG. 2 is an XRD pattern of hierarchical tungsten trioxide prepared in example 1 of the present invention;
FIG. 3 is an SEM photograph (magnification of 50000 times) of a hierarchical tungsten trioxide film prepared in example 2 of the present invention;
FIG. 4 is an XRD pattern of hierarchical tungsten trioxide prepared in example 2 of the present invention;
FIG. 5 is an SEM photograph (magnification of 50000 times) of hierarchical tungsten trioxide prepared in example 3 of the present invention;
FIG. 6 is an XRD pattern of hierarchical tungsten trioxide prepared according to example 3 of the present invention;
FIG. 7 is an SEM photograph (magnification of 50000) of a product obtained in comparative example 1 of the present invention;
FIG. 8 is an SEM photograph (magnification of 50000) of a product obtained in comparative example 2 of the present invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention are clearly and completely described below, and it is obvious that the described embodiments are a part of the embodiments of the present invention, but not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Unless otherwise specified, the test reagents and materials used in the examples of the present invention are commercially available.
Unless otherwise specified, the technical means used in the examples of the present invention are conventional means well known to those skilled in the art.
Example 1
The embodiment provides a preparation method of hierarchical tungsten trioxide, which comprises the following specific steps:
0.397g of tungsten hexachloride and 1.261g of oxalic acid are weighed out and dissolved in 100ml of ethanol, and the solution is placed on a magnetic stirrer with the rotating speed of 350r/min and stirred for 30min under the air atmosphere to obtain a yellow solution. Transferring the solution to a three-neck flask, placing the three-neck flask in an XH-300UL computer microwave ultrasonic ultraviolet light combined catalytic synthesizer (only using the microwave function), externally connecting a condensation reflux device, setting the microwave power to be 500W, heating for 45min by selecting a microwave power constant mode, and naturally cooling to the room temperature after the reaction is finished. Centrifuging to obtain precipitate, washing with ethanol repeatedly, and centrifuging for 2 times at 3000r/min for 5min. And (3) placing the cleaned product in an air drying box, setting the temperature to be 60 ℃, drying for 12h, taking out, placing in a muffle furnace, setting the temperature to be 500 ℃, preserving the heat for 1h, taking out, placing in air, and cooling to room temperature to obtain the tungsten trioxide with the hierarchical structure.
FIG. 1 is an SEM photograph of hierarchical tungsten trioxide prepared according to example 1, at a magnification of 50000, assembled from nanosheets; fig. 2 is an XRD spectrum of the hierarchical structure tungsten trioxide prepared in example 1, and it is found by comparison with a standard spectrum that the hierarchical structure tungsten trioxide prepared in example 1 of the present invention is monoclinic phase tungsten trioxide (PDF # 72-0677) and has no other impurity phase.
Example 2
The embodiment provides a preparation method of hierarchical tungsten trioxide, which comprises the following specific steps:
0.397g of tungsten hexachloride and 1.261g of oxalic acid are weighed out and dissolved in 100ml of ethanol, and the solution is placed on a magnetic stirrer with the rotating speed of 350r/min and stirred for 30min under the air atmosphere to obtain a yellow solution. Transferring the solution to a three-neck flask, placing the three-neck flask in an XH-300UL computer microwave ultrasonic ultraviolet light combined catalytic synthesizer, externally connecting a condensation reflux device, setting the microwave power to be 450W, selecting a microwave power constant mode, heating for 50min, and naturally cooling to room temperature after the reaction is finished. Centrifuging to obtain precipitate, washing with ethanol repeatedly, and centrifuging for 2 times at 3000r/min for 5min. And (3) placing the cleaned product in an air drying box, setting the temperature to be 60 ℃, drying for 12h, taking out, placing in a muffle furnace, setting the temperature to be 500 ℃, preserving the heat for 4h, taking out, placing in air, and cooling to room temperature to obtain the tungsten trioxide with the hierarchical structure.
FIG. 3 is an SEM photograph of the hierarchical structure tungsten trioxide prepared in example 2 at a magnification of 50000, which is assembled from nanosheets; fig. 4 is an XRD spectrum of the hierarchical structure tungsten trioxide prepared in example 2, and it is found by comparison with a standard spectrum that the hierarchical structure tungsten trioxide prepared in example 2 of the present invention is monoclinic phase tungsten trioxide (PDF # 72-0677) and has no other impurity phase.
Example 3
The embodiment provides a preparation method of tungsten trioxide with a hierarchical structure, which comprises the following specific steps:
0.397g of tungsten hexachloride and 1.261g of oxalic acid are weighed out and dissolved in 100ml of ethanol, and the solution is placed on a magnetic stirrer with the rotating speed of 350r/min and stirred for 30min under the air atmosphere to obtain a yellow solution. Transferring the solution to a three-neck flask, placing the three-neck flask in an XH-300UL computer microwave ultrasonic ultraviolet light combined catalytic synthesizer, externally connecting a condensation reflux device, setting the microwave power to be 600W, selecting a microwave power constant mode to heat for 40min, and naturally cooling to room temperature after the reaction is finished. Centrifuging to obtain precipitate, washing with ethanol repeatedly, and centrifuging for 2 times at 3000r/min for 5min. And (3) placing the cleaned product in an air drying box, setting the temperature to be 60 ℃, drying for 12h, taking out, placing in a muffle furnace, setting the temperature to be 500 ℃, preserving the heat for 6h, taking out, placing in air, and cooling to room temperature to obtain the tungsten trioxide with the hierarchical structure.
FIG. 5 is an SEM photograph of hierarchical tungsten trioxide prepared in example 3 at a magnification of 50000, assembled from nanosheets; fig. 6 is an XRD spectrum of the hierarchical-structure tungsten trioxide prepared in example 3, and it was found that the hierarchical-structure tungsten trioxide prepared in example 3 of the present invention was monoclinic-phase tungsten trioxide (PDF # 72-0677) and had no other impurity phase, as compared with the standard spectrum.
Comparative example 1
This comparative example provides a preparation process which differs from example 1 in that oxalic acid is replaced by an equimolar amount of urea.
As a result, the SEM image of the obtained product is shown in FIG. 7, which is 50000 times at magnification. From the SEM image, the product obtained by using urea as the shape control agent is irregular spherical in shape and is not self-assembled by nano sheets to form a hierarchical structure.
Comparative example 2
This comparative example provides a production method, which is different from example 2 in that the muffle furnace setting temperature was changed from 500 ℃ to 600 ℃.
As a result, the SEM image of the obtained product is shown in FIG. 8, which is 50000 times magnification. As can be seen from the SEM image, after the calcination temperature is raised to 600 ℃, the obtained product has irregular appearance and is not a hierarchical structure formed by self-assembly of nano sheets.
Finally, it should be noted that: the above examples are only intended to illustrate the technical solution of the present invention, but not to limit it; although the present invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some technical features may be equivalently replaced; and such modifications or substitutions do not depart from the spirit and scope of the corresponding technical solutions of the embodiments of the present invention.
Claims (4)
1. A method for preparing hierarchical tungsten trioxide by microwave assistance is characterized by comprising the steps of obtaining a tungsten trioxide precursor by a microwave-assisted precipitation method, and calcining the tungsten trioxide precursor;
in the microwave-assisted precipitation method, tungsten hexachloride and oxalic acid are dispersed in ethanol for reaction; the concentration of the tungsten hexachloride is 0.005-0.025mol/L, and the concentration of the oxalic acid is 0.05-0.20mol/L;
heating with constant microwave power in the microwave-assisted precipitation method, wherein the microwave power is 300 to 600W, and the heating time is 30 to 60min;
the calcining temperature is 400 to 550 ℃.
2. The microwave-assisted preparation method of hierarchical tungsten trioxide according to claim 1, characterized in that the concentration of the tungsten hexachloride is 0.01mol/L and the concentration of the oxalic acid is 0.1mol/L.
3. The microwave-assisted method for preparing the hierarchical tungsten trioxide as claimed in claim 1, wherein the calcining temperature is 500 ℃, and the temperature is kept for 1 to 6h.
4. The microwave-assisted method for preparing hierarchical tungsten trioxide according to claim 1, characterized by comprising the following steps:
s1, dispersing tungsten hexachloride and oxalic acid in ethanol, and stirring in an air atmosphere to obtain a precursor solution;
s2, performing microwave heating on the precursor solution at normal temperature and normal pressure, wherein the reactor is externally connected with a condensation reflux device, the microwave power is 300 to 600W, and the heating time is 30 to 60min;
s3, standing and cooling to room temperature after the reaction is finished, carrying out centrifugal separation on a reaction product, repeatedly washing and centrifuging the obtained solid substance by using an organic solvent, and drying for later use;
and S4, calcining the dried product, setting the temperature to be 500 ℃, keeping the temperature for 1 to 6 hours, taking out the product, and cooling the product in the air to room temperature to obtain the catalyst.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102757095A (en) * | 2011-04-29 | 2012-10-31 | 北京化工大学 | Tungsten oxide nanoflake self-assembly nanosphere and application method and application of tungsten oxide nanoflake self-assembly nanosphere |
| CN105271419A (en) * | 2015-09-30 | 2016-01-27 | 南京理工大学 | Preparation method of tungstic oxide nanosheet self-assembled micro-nano flower-balls |
| CN107117831A (en) * | 2017-05-26 | 2017-09-01 | 桂林理工大学 | A kind of WO3The preparation method of nano-chip arrays |
| CN108083341A (en) * | 2018-01-30 | 2018-05-29 | 陕西科技大学 | A kind of preparation method of the monoclinic phase tungstic acid with Lacking oxygen |
| JP2019142760A (en) * | 2018-02-16 | 2019-08-29 | 住友金属鉱山株式会社 | Method for producing tungsten trioxide |
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- 2021-04-02 CN CN202110361907.0A patent/CN113184912B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102757095A (en) * | 2011-04-29 | 2012-10-31 | 北京化工大学 | Tungsten oxide nanoflake self-assembly nanosphere and application method and application of tungsten oxide nanoflake self-assembly nanosphere |
| CN105271419A (en) * | 2015-09-30 | 2016-01-27 | 南京理工大学 | Preparation method of tungstic oxide nanosheet self-assembled micro-nano flower-balls |
| CN107117831A (en) * | 2017-05-26 | 2017-09-01 | 桂林理工大学 | A kind of WO3The preparation method of nano-chip arrays |
| CN108083341A (en) * | 2018-01-30 | 2018-05-29 | 陕西科技大学 | A kind of preparation method of the monoclinic phase tungstic acid with Lacking oxygen |
| JP2019142760A (en) * | 2018-02-16 | 2019-08-29 | 住友金属鉱山株式会社 | Method for producing tungsten trioxide |
Non-Patent Citations (2)
| Title |
|---|
| Growth mechanism of immobilized WO3 nanostructures in different solvents and their visible-light photocatalytic performance;Youshu Fan et al.;《Journal of Physics and Chemistry of Solids》;20200201;第140卷;109380 * |
| 分级结构WO3的制备及对SF6分解产物H2S的检测;孙墨杰 等;《微纳电子技术》;20201231;第57卷(第12期);1017-1022 * |
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