CN114772645A - Tungsten trioxide material with flower-like morphology and preparation method thereof - Google Patents
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Abstract
The invention provides a tungsten trioxide material with flower-shaped appearance and a preparation method thereof, and Na is used2WO4·2H2Taking O as a raw material and citric acid as an auxiliary agent to prepare a tungsten trioxide precursor solution; and sequentially carrying out microwave reaction and calcination treatment on the tungsten trioxide precursor solution to finally prepare the flower-shaped tungsten trioxide material. The preparation method controls Na2WO4·2H2The mass ratio of O to citric acid and the condition of microwave reaction can prepare NO2The gas has a flower-shaped tungsten trioxide material with excellent gas sensitivity. The tungsten trioxide material with the flower-shaped appearance has mutually overlapped sheet-shaped structures and presents the flower-shaped appearance, and the tungsten trioxide material with the flower-shaped appearance and NO are2Large contact area of gas, and thus to NO2The gas has a faster response speed and a lower detection limit.
Description
Technical Field
The invention belongs to the technical field of semiconductor metal oxide gas-sensitive materials, relates to a tungsten trioxide material, and particularly relates to a flower-shaped tungsten trioxide material and a preparation method thereof.
Background
Tungsten trioxide (WO)3) The material is a natural wide-bandgap semiconductor material, the bandgap is 2.62-3.25eV, and common crystal forms include a Monoclinic phase (Monoclinic), a Tetragonal phase (Tetragonal), a Hexagonal phase (Hexagonal) and the like. The structure of the tungsten trioxide material depends on the temperature, and the tungsten trioxide material is tetragonal system when the temperature is higher than 740 ℃, orthorhombic system when the temperature is 330-740 ℃, monoclinic system when the temperature is 17-330 ℃, and triclinic system when the temperature is-50-17 ℃.
The tungsten trioxide usually exists in a monoclinic structure, belongs to a P21/n space group, and has a melting point of 1473 ℃, a boiling point of 1750 ℃ and a specific gravity of 7.16g/cm3It sublimates obviously at 850 deg.C and is green when molten. Is stable in air, is insoluble in water and inorganic acids except hydrofluoric acid, and can be slowly dissolved in ammonia water and concentrated sodium hydroxide solution. As a typical semiconductor material, tungsten trioxide is considered as one of the most promising gas sensor sensitive materials, which has wide applications in both environmental detection and safety monitoring.
NO2Is a typical atmospheric pollution gas that contributes to the formation of secondary particulate matter of PM2.5, which in turn leads to the formation of haze. NO2And is also the main reason for the formation of acid rain and photochemical smog, which seriously damages the ecological environment. For human health, with NO2The nitrogen oxides, mainly nitrogen oxides, have a certain toxicity and are continuously exposed to NO in ppb level2The traditional Chinese medicine composition can cause harm to human bodies, mainly damage respiratory tracts and lungs, reduce the immunity of people and be difficult to resist respiratory diseases. Therefore, research and development on NO2A high performance gas sensor of (2) is necessary.
In recent years, various gas sensors including metal oxide gas sensors, solid electrolyte gas sensors, electrochemical gas sensors, and the like have been widely studied. At present, metal oxide semiconductor materials such as In2O3、WO3、SnO2ZnO and the like have been widely usedApplied in gas sensor, but because of the metal oxide semiconductor material to NO2The gas sensitivity is not good enough, and in practical application, the defects of low detection sensitivity, low response speed and the like still exist.
Disclosure of Invention
Aiming at the defects and shortcomings in the prior art, the invention aims to provide a tungsten trioxide material with a flower-shaped morphology and a preparation method thereof, and solves the problem that the tungsten trioxide material in the prior art is used for NO2The gas sensitivity of the gas needs to be improved.
In order to solve the technical problems, the invention adopts the following technical scheme to realize:
a method for preparing tungsten trioxide material with flower-like morphology from Na2WO4·2H2Preparing a tungsten trioxide precursor solution by taking O as a raw material and citric acid as an auxiliary agent; sequentially carrying out microwave reaction and calcination treatment on the tungsten trioxide precursor solution to finally prepare the flower-shaped tungsten trioxide material;
said Na2WO4·2H2The mass ratio of O to citric acid is (20-35): 6;
the microwave power of the microwave reaction is 300-500W, the reaction temperature is 150-170 ℃, and the reaction time is 50-80 min;
the flower-shaped tungsten trioxide material is a hexagonal tungsten trioxide material, crystals of the flower-shaped tungsten trioxide material belong to a P6/mmm space group, the flower-shaped tungsten trioxide material is composed of flower-shaped particles, and the average particle size of the flower-shaped particles is 2-3 mu m.
The invention also has the following technical characteristics:
preferably, said Na2WO4·2H2The mass ratio of O to citric acid is 30: 6.
preferably, the microwave power of the microwave reaction is 400W, the reaction temperature is 160 ℃, and the reaction time is 60 min.
The method specifically comprises the following steps:
preparing a tungsten trioxide precursor solution;
na is mixed with2WO4·2H2Dissolving O in water, adding citric acid, and stirring to Na2WO4·2H2After O and citric acid are completely dissolved, dropwise adding a pH regulator to regulate the pH value, and continuously stirring for 25-40 min after the pH value is regulated to prepare a tungsten trioxide precursor solution;
preparing a tungsten trioxide solid precursor;
carrying out microwave reaction on the tungsten trioxide precursor solution prepared in the step one, preparing a solid A after the microwave reaction is finished, and centrifugally washing and drying the solid A to prepare a tungsten trioxide solid precursor;
preparing a flower-shaped tungsten trioxide material;
calcining the tungsten trioxide solid precursor prepared in the step two to prepare a flower-shaped tungsten trioxide material after the calcining treatment is finished; the reaction temperature of the calcination treatment is 350-390 ℃, the reaction temperature rise rate is 4-6 ℃/min, and the reaction heat preservation time is 2-3 h.
Specifically, in the first step, the pH regulator is 3mol/L hydrochloric acid solution.
Specifically, in the step one, the pH value is adjusted to 0.8-1.2 during the pH value adjustment.
Preferably, in the third step, the reaction temperature of the calcination treatment is 380 ℃, the reaction temperature rise rate is 5 ℃/min, and the reaction heat preservation time is 2 h.
The invention also discloses a flower-shaped tungsten trioxide material which is prepared by the preparation method of the flower-shaped tungsten trioxide material.
The invention also protects the tungsten trioxide material with the flower-shaped morphology as a gas sensor material for NO2Use in a gas sensor.
Compared with the prior art, the invention has the beneficial technical effects that:
the invention relates to a preparation method of a flower-shaped tungsten trioxide material, which uses Na2WO4·2H2O as raw material and lemonPreparing a tungsten trioxide precursor solution by using citric acid as an auxiliary agent; and sequentially carrying out microwave reaction and calcination treatment on the tungsten trioxide precursor solution to finally prepare the flower-shaped tungsten trioxide material. The preparation method controls Na2WO4·2H2The mass ratio of O to citric acid and the conditions of microwave reaction can prepare NO2The gas has excellent gas sensitivity and is a tungsten trioxide material with flower-shaped appearance.
The preparation method of the flower-shaped tungsten trioxide material has the advantages of simple process, short preparation period, low cost and the like.
(III) the flower-shaped tungsten trioxide material has a sheet-shaped structure which is overlapped with each other, and shows a flower-shaped appearance, because the flower-shaped tungsten trioxide material and NO are in the flower-shaped appearance2Large contact area of gas, and therefore to NO2The gas has a faster response speed and a lower detection limit.
(IV) the tungsten trioxide material with flower-shaped morphology of the invention is used as a gas sensor material for NO2In the gas sensor, NO can be shortened2Response time and recovery time of gas sensor, reduction of NO2Detection limit of gas sensor, i.e. capable of increasing NO2Performance of the gas sensor.
Drawings
Fig. 1 is an SEM image of the flower-like morphology tungsten trioxide material of example 1.
Fig. 2 is an XRD pattern of the flower-like morphology tungsten trioxide material of example 1.
FIG. 3 is a Raman spectrum of the tungsten trioxide material with flower-like morphology in example 1.
Fig. 4 is an SEM image of the tungsten trioxide material in comparative example 1.
Fig. 5 is an SEM image of the tungsten trioxide material in comparative example 2.
Fig. 6 is an SEM image of the tungsten trioxide material in comparative example 3.
Fig. 7 is an SEM image of the tungsten trioxide material in comparative example 4.
Fig. 8 is an SEM image of the tungsten trioxide material in comparative example 5.
Fig. 9 is an SEM photograph of the tungsten trioxide material in comparative example 6.
Fig. 10 is an XRD spectrum of the tungsten trioxide material in comparative examples 1 to 3, in which comparative example 1 represented by 1, comparative example 2 represented by 2, and comparative example 3 represented by 3.
Fig. 11 is an XRD spectrum of the tungsten trioxide material in comparative examples 4 to 6, in which 4 represents comparative example 4, 5 represents comparative example 5, and 6 represents comparative example 6.
FIG. 12 is NO for the flower-like shaped tungsten trioxide material of example 12A gas responsivity map.
FIG. 13 shows NO of the flower-like shaped tungsten trioxide material of example 12Gas dynamic responsivity map.
The technical solution of the present invention is further illustrated by the following examples.
Detailed Description
It should be noted that all the raw materials in the present invention, unless otherwise specified, all the raw materials known in the art are used.
The present invention is not limited to the following embodiments, and equivalent changes made on the basis of the technical solutions of the present invention fall within the scope of the present invention.
Example 1:
the embodiment provides a preparation method of a tungsten trioxide material with a flower-shaped morphology, which specifically comprises the following steps:
preparing a tungsten trioxide precursor solution;
0.4948g of Na were weighed2WO4·2H2O and 0.1000g of citric acid, weighed Na2WO4·2H2Dissolving O in 25mL of deionized water, adding weighed citric acid, and stirring until Na is formed2WO4·2H2After O and citric acid are completely dissolved, dropwise adding a pH regulator to regulate the pH value to 1.0, and continuously stirring for 30min after the pH value is regulated to prepare a tungsten trioxide precursor solution; the pH regulator is 3mol/L hydrochloric acid solution.
Preparing a tungsten trioxide solid precursor;
putting the tungsten trioxide precursor solution prepared in the first step into a microwave oven for microwave reaction, wherein the microwave power of the microwave reaction is 400W, the reaction temperature is 160 ℃, the reaction time is 60min, and after the microwave reaction is finished, preparing a solid A; centrifugally washing and drying the solid A to prepare a tungsten trioxide solid precursor; the centrifugal washing comprises three conventional centrifugal washes.
Preparing a flower-shaped tungsten trioxide material;
placing the tungsten trioxide solid precursor prepared in the step two into a muffle furnace for calcination treatment, and preparing a flower-shaped tungsten trioxide material after the calcination treatment is finished; the reaction temperature of the calcination treatment is 380 ℃, the reaction temperature rise rate is 5 ℃/min, and the reaction heat preservation time is 2 h.
By adopting the preparation method of the flower-shaped tungsten trioxide material in the embodiment, as shown in fig. 1, the finally prepared tungsten trioxide material has a regular disc-shaped structure, the disc-shaped structure is thin and dispersed, the sheets are overlapped with one another, the tungsten trioxide material is composed of flower-shaped particles, the average particle size of the flower-shaped particles is about 2 μm, the maximum particle size is less than 5 μm, and the flower-shaped particles are uniform in size and distribution.
Fig. 2 is an XRD pattern of the flower-like tungsten trioxide material, and when fig. 2 is compared with a standard JCPDS No.33-1387 pattern, it is known that the XRD diffraction peak of the flower-like tungsten trioxide material finally obtained in the present example completely matches the standard pattern, and no other impurities are present, and it is known from fig. 2 that the flower-like tungsten trioxide material is a hexagonal phase tungsten trioxide material having a lattice constant of a-b-7.298 and c-3.899, and the crystals thereof correspond to a P6/mmm space group, and the diffraction peaks (100), (001), (110), (101), (200), (111), (201), (220), (202), (221), (400) and (401) in the range of 10-80degrees are most significant, and the diffraction peaks are strong and narrow, indicating that the crystallinity of the flower-like tungsten trioxide material is high.
As is clear from FIG. 3, the Raman spectrum of the tungsten trioxide material having a flower-like morphology was 200cm-1The following are providedThe wave band is caused by lattice vibration and is 253.1cm-1The observed Raman peak at (A) can correspond to the delta (O-W-O) deformation vibration mode at 692.7cm-1And 817.6cm-1The Raman peak at (A) is the stretching vibration mode corresponding to v (O-W-O). All of the raman peaks correspond to a characteristic raman peak of a hexagonal phase tungsten trioxide material, and it is explained that the flower-like morphology tungsten trioxide material belongs to the hexagonal phase tungsten trioxide material, and the results are consistent with the observation results in fig. 2.
In this embodiment, the gas-sensitive performance test is performed on the tungsten trioxide material with the flower-like morphology, and the gas-sensitive performance test adopts formula i to represent the gas responsivity of the material:
in the formula I:
s represents the gas responsivity of the material;
Rfindicating exposure of gas sensitive devices to NO2The resistance value of time is in units of omega;
R0indicating exposure of gas-sensitive devices to N2The resistance value in Ω.
The results of the gas-sensitive performance test of the flower-shaped tungsten trioxide material are shown in fig. 12 and 13.
As can be seen from FIG. 12, NO was observed at 200 ℃2The tungsten trioxide material with flower-shaped morphology is aligned to NO under the condition that the gas concentration is 1ppm2Has a significant response to NO2The gas responsiveness reached 2.8 and the response/recovery time reached 11/28 s. As can be seen from the combination of FIG. 1, the tungsten trioxide material with flower-like morphology forms a relatively dispersed sheet-like structure, and the sheets are overlapped to present a flower-like morphology, which is beneficial for the tungsten trioxide material and NO2The gases are fully contacted.
As can be seen from FIG. 13, with NO2The gas response of the flower-shaped tungsten trioxide material is reduced due to the reduction of the concentration, and the flower-shaped tungsten trioxide material can detect NO at the concentration of 20ppb at the temperature of 200 DEG C2Gas, and the noise of the curve is very small at this time, the gas responsivity can reach 0.4.
Comparative example 1:
this comparative example shows a method of producing a tungsten trioxide material that is substantially the same as the method of example 1, except that no citric acid is added in step one.
With the method of manufacturing the tungsten trioxide material in this comparative example, as shown in fig. 4 and 10, the finally manufactured tungsten trioxide material exhibits a hexagonal sheet structure having a surface with a plurality of prisms and a relatively thick thickness, and is composed of random agglomerates having different sizes and non-uniform distributions.
Comparative example 2:
this comparative example shows a method of producing a tungsten trioxide material which is substantially the same as that of example 1 except that in step one, the mass of citric acid was 0.2000 g.
With the method for producing the tungsten trioxide material in the present comparative example, as shown in fig. 5 and 10, the finally produced tungsten trioxide material exhibited a relatively polymerized sheet-like structure, and the sheets were fitted to each other with small gaps therebetween, and consisted of spherical particles having different sizes and non-uniform distribution.
Comparative example 3:
this comparative example shows a production method of a tungsten trioxide material which is substantially the same as that of example 1 except that in step one, the mass of citric acid was 0.3000 g.
By adopting the preparation method of the tungsten trioxide material in the comparative example, as shown in fig. 6 and 10, the finally prepared tungsten trioxide material has a random sheet structure, the sheet structure is dispersed, and a large number of small crystal grains appear around the tungsten trioxide material.
Comparative example 4:
this comparative example shows a method for producing a tungsten trioxide material, which is substantially the same as the production method of example 1 except that the reaction time of the microwave reaction in step two is 10 min.
With the method for producing the tungsten trioxide material in this comparative example, as shown in fig. 7 and 11, the finally produced tungsten trioxide material is composed of flocculent small grains which are small in size, unevenly distributed and aggregated together.
Comparative example 5:
this comparative example shows a method for producing a tungsten trioxide material, which is substantially the same as the production method of example 1 except that the reaction time of the microwave reaction in step two is 40 min.
With the method of producing the tungsten trioxide material in this comparative example, as shown in fig. 8 and 11, the finally produced tungsten trioxide material exhibits a relatively polymerized sheet-like structure, and the sheets are attached to each other with small gaps therebetween, and is composed of spherical particles having different sizes and non-uniform distributions.
Comparative example 6:
this comparative example shows a method for producing a tungsten trioxide material, which is substantially the same as the production method of example 1 except that the reaction time of the microwave reaction in step two is 100 min.
By adopting the preparation method of the tungsten trioxide material in the comparative example, as shown in fig. 9 and fig. 11, the finally prepared tungsten trioxide material presents a relatively polymerized sheet structure, the tungsten trioxide material is composed of irregular-shaped crystal grains, the tungsten trioxide material is hydrolyzed due to long-time reaction, and the irregular-shaped crystal grains are different in size and uneven in distribution and present a disordered appearance.
From example 1 and comparative examples 1 to 6, the following conclusions can be drawn:
(A) from example 1 and comparative examples 1 to 3, it can be seen that:
after 0.1000g of citric acid was added to example 1, the thickness of the sheet-like structure of the tungsten trioxide material was reduced, the sheet-to-sheet separation tendency was observed, and the sheet-like structure became loose, overlapped with each other and showed a flower-like appearanceIn example 1, the tungsten trioxide material with flower-like morphology has larger specific surface area and is beneficial to reacting with NO2The gases are fully contacted.
In comparative example 1, citric acid was not added, and the final oxide material sheet structure was thick and non-uniform in size. After the addition of 0.2000g and 0.3000g of citric acid in comparative example 2 and comparative example 3, respectively, the tungsten trioxide material began to polymerize and the size of the grains gradually became non-uniform, the sheet structure became irregular, and a large number of small grains began to adhere to the surface of the material, presenting a disordered morphology.
From the above analysis, it is found that in the method for producing a tungsten trioxide material having a flower-like morphology according to the present invention, Na is used for the production of the precursor solution2WO4·2H2The quality ratio of O and citric acid plays an important role in regulating the appearance of the product when Na is contained2WO4·2H2The mass ratio of O to citric acid is about 30: 6, good NO can be obtained2A flower-shaped tungsten trioxide material with gas-sensitive performance.
(B) From example 1 and comparative examples 4 to 6, it can be seen that:
the reaction time of the microwave reaction in example 1 is 60min, and the finally prepared flower-shaped tungsten trioxide material has uniformly dispersed crystal grains and uniform crystal grain size.
In comparative example 4, the reaction time of the microwave reaction was 10min, and the finally obtained oxide material could not form a sheet structure and showed a flocculent appearance consisting of small particles. In comparative example 4, the reaction time of the microwave reaction was 40min, and the finally obtained oxide material started to have a sheet-like structure, but was relatively uniform from sheet to sheet and was not uniform in size. In comparative example 4, the reaction time of the microwave reaction was 100min, and the oxide material finally obtained showed hydrolysis, and a large number of small grains were filled in the gaps of the material, thus showing a disordered morphology.
As can be seen from the above analysis, in the method for preparing the tungsten trioxide material with flower-like morphology according to the present invention, the reaction time of the microwave reaction has a great influence on the morphology of the product, and when the reaction time of the microwave reaction is 60minCan produce good NO2A flower-shaped tungsten trioxide material with gas-sensitive performance.
Claims (9)
1. The preparation method of the tungsten trioxide material with flower-shaped appearance is characterized in that Na is used2WO4·2H2Preparing a tungsten trioxide precursor solution by taking O as a raw material and citric acid as an auxiliary agent; sequentially carrying out microwave reaction and calcination treatment on the tungsten trioxide precursor solution to finally prepare the flower-shaped tungsten trioxide material;
said Na2WO4·2H2The mass ratio of O to citric acid is (20-35): 6;
the microwave power of the microwave reaction is 300-500W, the reaction temperature is 150-170 ℃, and the reaction time is 50-80 min;
the flower-shaped tungsten trioxide material is a hexagonal phase tungsten trioxide material, crystals of the flower-shaped tungsten trioxide material belong to a P6/mmm space group, the flower-shaped tungsten trioxide material is composed of flower-shaped particles, and the average particle size of the flower-shaped particles is 2-3 mu m.
2. The method for preparing tungsten trioxide material with flower-like morphology according to claim 1, characterized in that the Na is2WO4·2H2The mass ratio of O to citric acid is 30: 6.
3. the method for preparing tungsten trioxide material with flower-like morphology according to claim 1, wherein the microwave power of the microwave reaction is 400W, the reaction temperature is 160 ℃, and the reaction time is 60 min.
4. The method for preparing the flower-shaped tungsten trioxide material as claimed in claim 1, which comprises the following steps:
preparing a tungsten trioxide precursor solution;
na is mixed with2WO4·2H2Dissolving O in water, adding citric acid, and stirring to Na2WO4·2H2After the O and the citric acid are completely dissolved, dropwise adding a pH regulator to regulate the pH value, and continuously stirring for 25-40 min after the pH value is regulated to prepare a tungsten trioxide precursor solution;
preparing a tungsten trioxide solid precursor;
carrying out microwave reaction on the tungsten trioxide precursor solution prepared in the step one, preparing a solid A after the microwave reaction is finished, and centrifugally washing and drying the solid A to prepare a tungsten trioxide solid precursor;
preparing a flower-shaped tungsten trioxide material;
calcining the tungsten trioxide solid precursor prepared in the step two to prepare a flower-shaped tungsten trioxide material after the calcining treatment is finished; the reaction temperature of the calcination treatment is 350-390 ℃, the reaction temperature rise rate is 4-6 ℃/min, and the reaction heat preservation time is 2-3 h.
5. The method for preparing the flower-like tungsten trioxide material according to claim 4, wherein in the first step, the pH regulator is 3mol/L hydrochloric acid solution.
6. The method for preparing the flower-shaped tungsten trioxide material according to claim 4, wherein in the first step, the pH value is adjusted to 0.8-1.2 during the pH value adjustment.
7. The method for preparing the flower-like tungsten trioxide material according to claim 4, wherein the calcining is carried out at a reaction temperature of 380 ℃, a reaction temperature rise rate of 5 ℃/min and a reaction holding time of 2 h.
8. The flower-shaped tungsten trioxide material characterized by being produced by the production method for the flower-shaped tungsten trioxide material according to any one of claims 1 to 7.
9. Flower-like shaped tungsten trioxide material according to claim 8 as gas sensor material for NO2Gas (es)Use in a sensor.
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