CN108128806A - A kind of preparation method and applications of tungsten oxide-graphene composite material - Google Patents
A kind of preparation method and applications of tungsten oxide-graphene composite material Download PDFInfo
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- CN108128806A CN108128806A CN201711365715.7A CN201711365715A CN108128806A CN 108128806 A CN108128806 A CN 108128806A CN 201711365715 A CN201711365715 A CN 201711365715A CN 108128806 A CN108128806 A CN 108128806A
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Abstract
A kind of preparation method of tungsten oxide graphene composite material is realized by the following method, first, graphene oxide is prepared using modified Hummers methods, by the dispersion of obtained graphene oxide in aqueous solution, tungsten source is added in thereto, after stirring evenly, then suitable acetone is added in into mixed liquor, adjust the polarity of reaction system；Secondly, continue to stir above-mentioned mixed liquor, after a period of time, mixed liquor is transferred in microwave reactor, is reacted, after a few minutes, take out reactant；Finally, reactant obtained above is subjected to washing centrifugation, tungsten oxide graphene composite material is isolated, after drying, the composite material is placed in porcelain boat, it is put into Muffle furnace to be heat-treated, after treatment, room temperature to be cooled to the furnace both obtains final products, tungsten oxide graphene composite material prepared by the present invention has fabulous gas detection sensitivity, especially to acetone, minimum detection limit can reach 20ppb, and with good stability.
Description
Technical field
The present invention relates to a kind of preparation fields of advanced function composite material, and in particular to a kind of tungsten oxide-graphene is multiple
The preparation method and applications of condensation material.
Background technology
Tungsten oxide is a kind of important semi-conducting material, due to its smaller band gap so that it has physico well
Property is learned, is always the hot spot of research, is such as widely used in the gentle body context of detection of photocatalysis, but tungsten oxide material is certainly
Body is difficult to overcome the problems, such as there is also some, although such as its band gap with very little, the recombination rate pole of its electrons and holes
Height, this causes tungsten oxide material at work, generally requires higher operating temperature, and for gas context of detection, spirit
Sensitivity can not meet the needs of present situation.
In order to further expand the application range of tungsten oxide, scientific research personnel employs a variety of methods and is attempted, such as to it
Be doped, coat etc., wherein, Xiaoqiang An et al. exist《Material physical chemistry》（J. Mater. Chem）On deliver
Entitled " WO3 nanorods/graphene nanocomposites for high-efficiency visible-light-
driven photocatalysis and NO2 The research article of gas sensing ", in this article, author uses hydro-thermal
Method has prepared the composite material of tungstic acid and graphene, when which is used for the detection of nitrogen dioxide gas,
It was found that the WO that its performance ratio is pure3Nanometer rods are 25 times high, and minimum detection limit has reached 25ppb, have the detection of good gas should
Use prospect.But the hydrothermal method used in this method is reacted 24 hours at 180 DEG C, this so that this method energy consumption is high,
And the yield of product is also greatly limited.Chinese patent（CN106872063A）Disclose a kind of tubulose tungsten oxide-stone
The preparation method and applications of black alkene composite material, and specifically disclose preparation method：First, by graphite oxidation into graphite oxide
Powder；2nd, by graphite oxide powder ultrasonic disperse in normal propyl alcohol, tungsten hexachloride is then added in, carries out hydro-thermal reaction；3rd, pH is adjusted
Then value adds in 50% hydrazine hydrate aqueous solution, is reacted in oil bath, is dried after carrying out eccentric cleaning after reaction to 9~10,
Black powder, i.e. tubulose tungsten oxide-graphene composite material are obtained, and can be answered as the temperature-sensing property material of temperature sensor
By the use of, as gas sensor sensitive material application or be used as photocatalytic degradation material application.But this method equally uses hydro-thermal
Method prepare composite material, and be to be obtained after reacting 10-14h at 150 DEG C~250 DEG C, and come from the SEM photograph of product
It sees, structure is very uneven, this can cause large effect to the final performance of product.
Invention content
Based on the above, the present invention proposes a kind of preparation for preparing tungsten oxide-graphene composite material rapidly and efficiently
Method, and applicant, by verification experimental verification, which has extraordinary gas detectability, especially
It shows acetone excellent detection limit.
The preparation method of tungsten oxide-graphene composite material of the present invention is realized by the following method, and first, uses
Modified Hummers methods prepare graphene oxide, by the dispersion of obtained graphene oxide in aqueous solution, add in tungsten thereto
Source after stirring evenly, then adds in suitable acetone into mixed liquor, adjusts the polarity of reaction system；Secondly, continue to stir above-mentioned
After a period of time, mixed liquor is transferred in microwave reactor, is reacted for mixed liquor, after a few minutes, takes out reactant；Most
Afterwards, reactant obtained above is subjected to washing centrifugation, isolates tungsten oxide-graphene composite material, it is after drying, this is compound
Material is placed in porcelain boat, is put into Muffle furnace and is heat-treated, after treatment, room temperature to be cooled to the furnace both finally produce
Product.
Specifically, the present invention is the preparation for being achieved through the following technical solutions tungsten oxide-graphene composite material,
The first step prepares large stretch of graphene oxide using modified Hummers methods, and the radial dimension of wherein graphene oxide sheet exists
Between 50-100 μm, above-mentioned graphene oxide is configured to the water solution A of a concentration of 0.5-2mg/ml；
Aforementioned oxidation graphene aqueous solution A is placed on magnetic stirring apparatus, is stirred using fusiformis magneton by second step,
Middle mixing speed is 100-500rpm, and under continuous stirring, weighing good dissolving in advance, tungsten source is added dropwise into solution A in ethanol
In, continue to stir, then add suitable acetone into mixed solution again, adjust the polarity of reaction solution, finally obtain reaction
Liquid B；
Third walks, and reaction solution B is transferred in microwave reactor and carries out microwave reaction, after reaction, obtained product is washed
Wash centrifugal treating, above-mentioned product dried at 100-150 DEG C, then the product after drying is put into porcelain boat, in Muffle furnace into
After row heat treatment, final product is obtained after the product of furnace cooling is ground.
Further, preferred technical solution is the one kind of tungsten source in tungsten hexachloride, sodium tungstate in the step 2,
The ethanol solution concentration in tungsten source is 25-100mg/ml.
Further, it is the 1- of overall reaction liquid product that preferred technical solution, which is the additive amount of acetone in the step two,
5%。
Further, preferred technical solution is microwave reactor in the step three, and power is 100-500W, instead
5-20min between seasonable.
Further, preferred technical solution is that heat treatment refers in nitrogen atmosphere in the step three, with 5-15
DEG C/heating rate of min rises to 600-800 DEG C of heat preservation 0.5-2h by room temperature.
The principle of the present invention is, firstly, since tungsten oxide is a kind of semi-conducting material, electric conductivity is greatly limited
System, in gas sensor application field, this can influence its detection limit, accordingly, since grapheme material has extraordinary electronics
It can not only be improved the electric conductivity of tungsten oxide, and high ratio by mobility, great specific surface area with tungsten oxide after compound
Surface area can also adsorb more molecules, this causes the composite material to have good performance, in addition, applicant is also by changing
Become reaction condition, especially into acetone, change the polarity of reaction system, the preparation of this composite material to obtaining has greatly
It influences, and last heat treatment process, on the one hand it is that graphene oxide is reduced to graphene, on the other hand can then improves this
The crystal property of composite material, applicant did contrast test, the composite material after Overheating Treatment, and performance is compared to untreated
Material be greatly improved.
Compared with prior art, the present invention has technique effect beneficial below：
1）, the unused highly energy-consuming of the present invention, low-producing hydro-thermal method prepare tungsten oxide graphene composite material, but used micro-
Wave-process of thermal treatment, it is simple, fast and efficient to prepare the beneficial composite material of performance；
2）, the present invention in the reaction system introduce acetone adjust reaction system polarity, one is produced to the performance of final product
Fixed influence；
3）, the tungsten oxide graphene composite material for preparing of the present invention there is fabulous gas detection sensitivity, especially to acetone,
Minimum detection limit can reach 20ppb, and with good stability.
Description of the drawings
The XRD spectrum of tungsten oxide prepared by Fig. 1 present invention；
The detection curve of graphene complex material prepared by Fig. 2 present invention as sensor material to acetone, minimum can
To reach 20ppb.
Specific embodiment
Embodiment 1
Large stretch of graphene oxide that average piece diameter is 50 μm is prepared using modified Hummers methods, above-mentioned graphene oxide is matched
The water solution A of a concentration of 0.5mg/ml is made；Graphene oxide water solution A is placed on magnetic stirring apparatus, uses fusiformis magnetic
Son is stirred, and wherein mixing speed is 100rpm, and under continuous stirring, the tungsten hexachloride ethanol solution of 25mg/ml is dripped
It adds in solution A, continues to stir, then add the acetone of 1mL into mixed solution again, adjust the polarity of reaction solution, obtain
Reaction solution B；Reaction solution B is transferred in the microwave reactor of 200W and carries out microwave reaction, reaction time 5min, reaction terminates
Afterwards, obtained product is washed into centrifugal treating, above-mentioned product is dried at 100 DEG C, then the product after drying is put into porcelain boat,
800 DEG C are warming up in Muffle furnace with the heating rate of 5 DEG C/min to be heat-treated, after keeping the temperature 1h, by the product of furnace cooling
Final product is obtained after grinding.
Embodiment 2
Large stretch of graphene oxide that average piece diameter is 100 μm is prepared using modified Hummers methods, above-mentioned graphene oxide is matched
The water solution A of a concentration of 1mg/ml is made；Graphene oxide water solution A is placed on magnetic stirring apparatus, uses fusiformis magneton
It is stirred, wherein mixing speed is 100rpm, and under continuous stirring, the tungsten hexachloride ethanol solution of 50mg/ml is added dropwise
Into in solution A, continue to stir, then add the acetone of 1.5mL into mixed solution again, adjust the polarity of reaction solution, obtain
Reaction solution B；Reaction solution B is transferred in the microwave reactor of 200W and carries out microwave reaction, reaction time 7min, reaction terminates
Afterwards, obtained product is washed into centrifugal treating, above-mentioned product is dried at 100 DEG C, then the product after drying is put into porcelain boat,
800 DEG C are warming up in Muffle furnace with the heating rate of 5 DEG C/min to be heat-treated, after keeping the temperature 1h, by the product of furnace cooling
Final product is obtained after grinding.
Embodiment 3
Large stretch of graphene oxide that average piece diameter is 100 μm is prepared using modified Hummers methods, above-mentioned graphene oxide is matched
The water solution A of a concentration of 2mg/ml is made；Graphene oxide water solution A is placed on magnetic stirring apparatus, uses fusiformis magneton
It is stirred, wherein mixing speed is 100rpm, and under continuous stirring, the tungsten hexachloride ethanol solution of 100mg/ml is added dropwise
Into in solution A, continue to stir, then add the acetone of 1.5mL into mixed solution again, adjust the polarity of reaction solution, obtain
Reaction solution B；Reaction solution B is transferred in the microwave reactor of 500W and carries out microwave reaction, reaction time 10min, reaction knot
Obtained product is washed centrifugal treating, above-mentioned product is dried at 100 DEG C, then the product after drying is put into porcelain boat by Shu Hou
In, in Muffle furnace being warming up to 800 DEG C with the heating rate of 5 DEG C/min is heat-treated, after keeping the temperature 1h, by the production of furnace cooling
Final product is obtained after object grinding.
Claims (7)
1. a kind of tungsten oxide-graphene composite material, it is characterised in that：The composite material is by graphene and WO3It forms,
And pass through microwave combination heat-treating methods and be prepared.
2. a kind of preparation method of tungsten oxide-graphene composite material according to claim 1, it is characterised in that：First
Step prepares large stretch of graphene oxide using modified Hummers methods, and wherein the radial dimension of graphene oxide sheet is at 50-100 μm
Between, above-mentioned graphene oxide is configured to the water solution A of a concentration of 0.5-2mg/ml；
Aforementioned oxidation graphene aqueous solution A is placed on magnetic stirring apparatus, is stirred using fusiformis magneton by second step,
Middle mixing speed is 100-500rpm, and under continuous stirring, weighing good dissolving in advance, tungsten source is added dropwise into solution A in ethanol
In, continue to stir, then add suitable acetone into mixed solution again, adjust the polarity of reaction solution, finally obtain reaction
Liquid B；
Third walks, and reaction solution B is transferred in microwave reactor and carries out microwave reaction, after reaction, obtained product is washed
Wash centrifugal treating, above-mentioned product dried at 100-150 DEG C, then the product after drying is put into porcelain boat, in Muffle furnace into
After row heat treatment, final product is obtained after the product of furnace cooling is ground.
3. a kind of preparation method of tungsten oxide-graphene composite material according to claim 2, it is characterised in that：It is described
The one kind of tungsten source in tungsten hexachloride, sodium tungstate in step 2, the ethanol solution concentration in tungsten source is 25-100mg/ml.
4. a kind of preparation method of tungsten oxide-graphene composite material according to claim 2, it is characterised in that：It is described
The additive amount of acetone is the 1-5% of overall reaction liquid product in step 2.
5. a kind of preparation method of tungsten oxide-graphene composite material according to claim 2, it is characterised in that：It is described
Microwave reactor in step 3, power are 100-500W, reaction time 5-20min.
6. a kind of preparation method of tungsten oxide-graphene composite material according to claim 2, it is characterised in that：It is described
Heat treatment refers in nitrogen atmosphere in step 3, and 600-800 DEG C of heat preservation is risen to by room temperature with the heating rate of 5-15 DEG C/min
0.5-2h。
7. a kind of tungsten oxide-graphene composite material according to claim 2, it is characterised in that：Its detection to acetone
Lower limit is 20ppb.
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| CN201711365715.7A CN108128806B (en) | 2017-12-18 | 2017-12-18 | Preparation method and application of tungsten oxide-graphene composite material |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US10888845B1 (en) * | 2020-07-17 | 2021-01-12 | King Abdulaziz University | Graphene-tungsten oxide-metal boride/hydroxide photocatalysts, and methods for organic pollutant degradation and hydrogen production |
| CN114471625A (en) * | 2021-11-30 | 2022-05-13 | 东北农业大学 | Preparation method and application of nickel selenide/tungsten trioxide/graphene photocatalytic composite material |
| CN115159577A (en) * | 2022-05-30 | 2022-10-11 | 沈阳工业大学 | Three-dimensional tungsten oxide material composed of nano-fibers and preparation method thereof |
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| CN104807860A (en) * | 2014-12-23 | 2015-07-29 | 郑州轻工业学院 | Flower-like nano-WO3/graphene composite gas-sensitive material and preparation method and application thereof |
| CN106872063A (en) * | 2017-01-17 | 2017-06-20 | 中国电子科技集团公司第四十九研究所 | A kind of preparation method and application of tubulose tungsten oxide graphene composite material |
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| CN104807860A (en) * | 2014-12-23 | 2015-07-29 | 郑州轻工业学院 | Flower-like nano-WO3/graphene composite gas-sensitive material and preparation method and application thereof |
| CN106872063A (en) * | 2017-01-17 | 2017-06-20 | 中国电子科技集团公司第四十九研究所 | A kind of preparation method and application of tubulose tungsten oxide graphene composite material |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US10888845B1 (en) * | 2020-07-17 | 2021-01-12 | King Abdulaziz University | Graphene-tungsten oxide-metal boride/hydroxide photocatalysts, and methods for organic pollutant degradation and hydrogen production |
| CN114471625A (en) * | 2021-11-30 | 2022-05-13 | 东北农业大学 | Preparation method and application of nickel selenide/tungsten trioxide/graphene photocatalytic composite material |
| CN115159577A (en) * | 2022-05-30 | 2022-10-11 | 沈阳工业大学 | Three-dimensional tungsten oxide material composed of nano-fibers and preparation method thereof |
| CN115159577B (en) * | 2022-05-30 | 2023-08-25 | 沈阳工业大学 | Three-dimensional tungsten oxide material composed of nanofibers and preparation method thereof |
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