CN111072067B - Ammonium tungsten bronze hollow microsphere and preparation method thereof - Google Patents
Ammonium tungsten bronze hollow microsphere and preparation method thereof Download PDFInfo
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Abstract
The invention provides an ammonium tungsten bronze hollow microsphere and a preparation method thereof, belonging to the technical field of preparation of inorganic materials. The preparation method provided by the invention comprises the following steps: mixing tungsten trioxide, thiourea and water, carrying out hydrothermal reaction, and then sequentially separating and drying to obtain the ammonium tungsten bronze hollow microsphere. According to the invention, tungsten trioxide and thiourea are used as raw materials, and the ammonium tungsten bronze hollow microsphere is prepared by a hydrothermal method, so that the prepared ammonium tungsten bronze hollow microsphere has high purity, good crystallization property and dispersibility, and concentrated particle size distribution.
Description
Technical Field
The invention belongs to the technical field of preparation of inorganic materials, and particularly relates to an ammonium tungsten bronze hollow microsphere and a preparation method thereof.
Background
Ammonium tungsten bronze ((NH)4)xWO3) Is an important member of tungsten bronze compound, and has unique tunnel structure, wherein tungsten ions are represented by W6+And W5+The mixed valence state of (A) exists, and is more and more concerned by people because of having good application prospects in the fields of near infrared light absorption, catalysis, batteries, gas sensing, photoinduced and electrochromic devices and the like. However, the ammonium tungsten bronze is structurally defined by relatively large-sized gaps NH4 +Intercalation of cations into WO6The gaps among the octahedral meshes are formed, so that the octahedral meshes have larger structural distortion, and the synthetic preparation of the octahedral meshes is difficult to prepare, particularly the ammonium tungsten bronze with a specific morphology.
At present, the preparation methods of ammonium tungsten bronze proposed at home and abroad mainly comprise a solid-phase thermal decomposition method, a hydrothermal and solvothermal synthesis method. Although the solid-phase thermal decomposition method can be used for large-scale production, the required reaction temperature is higher (usually more than 500 ℃), the obtained product has overlarge particle size and serious agglomeration, and the morphology of the product is difficult to control and impurities are easy to introduce. So far, only a few kinds of ammonium tungsten bronzes with regular shapes are successfully prepared by people by adopting a hydrothermal or solvothermal method, such as ammonium tungsten bronze nanocrystals, nanocubes and nanorods, however, no literature report is found on the preparation of the ammonium tungsten bronze hollow microspheres. As is well known, the performance of the material is closely related to the morphology of the material, so that the preparation of the ammonium tungsten bronze with different morphologies has important significance for regulating and expanding the performance application of the material.
Disclosure of Invention
In view of the above, the invention aims to provide an ammonium tungsten bronze hollow microsphere and a preparation method thereof. The ammonium tungsten bronze hollow microsphere prepared by the preparation method provided by the invention has the advantages of high purity, good crystallization property and dispersibility and concentrated particle size distribution.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a preparation method of ammonium tungsten bronze hollow microspheres, which comprises the following steps:
mixing tungsten trioxide, thiourea and water, carrying out hydrothermal reaction, and then sequentially separating and drying to obtain the ammonium tungsten bronze hollow microsphere.
Preferably, the molar ratio of the tungsten trioxide to the thiourea is 1 (2.7-3.3).
Preferably, the molar concentration of the tungsten trioxide in the mixed solution of the tungsten trioxide, thiourea and water is 0.08-0.14 mol/L.
Preferably, the molar concentration of the thiourea in the mixed solution of the tungsten trioxide, the thiourea and the water is 0.29-0.36 mol/L.
Preferably, the temperature of the hydrothermal reaction is 190-210 ℃ and the time is 9-20 h.
Preferably, the drying temperature is 50-70 ℃, and the drying time is 6-10 h.
The invention also provides the ammonium tungsten bronze hollow microsphere prepared by the preparation method in the technical scheme, the ammonium tungsten bronze hollow microsphere takes a mixture of ammonium tungsten bronze nanoparticles and ammonium tungsten bronze nanorods as a shell, and the particle size of the ammonium tungsten bronze nanoparticles in the mixture of the ammonium tungsten bronze nanoparticles and the ammonium tungsten bronze nanorods is 30-160 nm; the length of the ammonium tungsten bronze nanorod is 0.4-1.8 mu m, and the diameter of the ammonium tungsten bronze nanorod is 20-140 nm.
Preferably, the particle size of the ammonium tungsten bronze hollow microsphere is 4-15 μm.
The invention provides a preparation method of ammonium tungsten bronze hollow microspheres, which comprises the following steps: mixing tungsten trioxide, thiourea and water, carrying out hydrothermal reaction, and then sequentially separating and drying to obtain the ammonium tungsten bronze hollow microsphere. The invention takes thiourea as raw material to carry out hydrolysis reaction under hydrothermal condition to generate NH3、H2S and CO2Gas, generated NH3Reacting with water to form ammonia water, reacting the ammonia water with tungsten trioxide to form ammonium paratungstate, and further reacting the ammonium paratungstate with the formed H2S, reacting to obtain ammonium tungsten bronze nanoparticles and ammonium tungsten bronze nanorods; CO produced2The gas plays the role of the nucleation aggregation points of the ammonium tungsten bronze nanoparticles and the ammonium tungsten bronze nanorods, serves as the center of a temporarily formed core-shell structure, and CO generated in the reaction solution2The gas can greatly promote the formation of a hollow spherical structure composed of ammonium tungsten bronze nanoparticles and ammonium tungsten bronze nanorods. The preparation method provided by the invention is simple to operate, low in production cost, good in repeatability and easy for large-scale production, and the prepared ammonium tungsten bronze hollow microspheres are high in purity, good in crystallization property and dispersibility and concentrated in particle size distribution. The embodiment result shows that the particle size of the ammonium tungsten bronze nanoparticles in the prepared ammonium tungsten bronze hollow microspheres is 30-160 nm, the length of the ammonium tungsten bronze nanorods is 0.4-1.8 mu m, and the diameter of the ammonium tungsten bronze nanorods is 20-140 nm. Particle size of ammonium tungsten bronze hollow microsphere4-15 μm, and has good crystallization property and dispersibility.
Drawings
The present invention will be described in further detail with reference to the accompanying drawings and specific embodiments.
FIG. 1 is an XRD pattern of ammonium tungsten bronze hollow microspheres prepared in example 1;
FIG. 2 is an SEM image at 1000 times of the ammonium tungsten bronze hollow microspheres prepared in example 1;
FIG. 3 is an SEM image at 20000 times of hollow ammonium tungsten bronze microspheres prepared in example 1;
FIG. 4 is an SEM photograph of the product prepared in example 4 at 100000 times;
figure 5 is an SEM image at 100000 x of the product prepared in example 5.
Detailed Description
The invention provides a preparation method of ammonium tungsten bronze hollow microspheres, which comprises the following steps:
mixing tungsten trioxide, thiourea and water, carrying out hydrothermal reaction, and then sequentially separating and drying to obtain the ammonium tungsten bronze hollow microsphere.
In the present invention, the raw materials used are all commercial products which are conventional in the art, unless otherwise specified.
In the present invention, the molar ratio of the tungsten trioxide to the thiourea is preferably 1 (2.7 to 3.3), and more preferably 1: 3. In the present invention, the molar concentration of the tungsten trioxide in the mixed solution of tungsten trioxide, thiourea and water is preferably 0.08 to 0.14mol/L, and more preferably 0.11 mol/L. In the present invention, the particle diameter of the tungsten trioxide is preferably 300nm or less. In the present invention, the tungsten trioxide is preferably prepared by a hydrothermal method, and the operation of the substrate of the hydrothermal method is not particularly limited in the present invention, and the conditions of the hydrothermal method well known to those skilled in the art can be adopted.
In the invention, the molar concentration of the thiourea in the mixed solution of the tungsten trioxide, the thiourea and the water is preferably 0.29-0.36 mol/L, and more preferably 0.32 mol/L.
In the invention, the temperature of the hydrothermal reaction is preferably 190-210 ℃, more preferably 200 ℃, and the time is preferably 9-20 h, more preferably 12 h. In the present invention, the hydrothermal reaction is preferably carried out in a stainless steel reaction vessel lined with polytetrafluoroethylene, and the filling ratio of the stainless steel reaction vessel is preferably 80%.
In the invention, thiourea is hydrolyzed under hydrothermal condition to generate NH3、H2S and CO2Gas, the reaction formula is shown as formula 1:
CH4N2S+2H2O→2NH3+H2S+CO2formula 1
Generated NH3The ammonia water can react with tungsten trioxide to generate ammonium paratungstate, and the reaction formula is shown as formula 2:
12WO3+10NH3+(n+5)H2O→5(NH4)2O·12WO3·nH2o formula 2
Ammonium paratungstate further reacts with H formed2S, reacting to obtain the ammonium tungsten bronze nanoparticles and the ammonium tungsten bronze nanorods, wherein the reaction formula is shown as formula 3:
5(NH4)2O·12WO3·nH2O+2xH2S→12(NH4)xWO3+(10-12x)NH3+2xSO2+(n+5-4x)H2o formula 3
CO produced2The gas plays the role of the nucleation aggregation points of the ammonium tungsten bronze nanoparticles and the ammonium tungsten bronze nanorods, serves as the center of a temporarily formed core-shell structure, and CO generated in the reaction solution2The gas can greatly promote the formation of a hollow spherical structure composed of ammonium tungsten bronze nanoparticles and ammonium tungsten bronze nanorods. Too low a hydrothermal reaction temperature may result in insufficient hydrolysis of thiourea, and too high a hydrothermal reaction temperature may result in CO release from hydrolysis of thiourea2When the gas is too violent, the formation of the ammonium tungsten bronze hollow microsphere structure is not facilitated by the gas. The invention effectively prepares the ammonium tungsten bronze nanoparticles and the ammonium tungsten bronze nanoparticles by controlling the dosage and concentration of the tungsten trioxide and the thiourea and the temperature of the hydrothermal reactionThe hollow microsphere structure formed by the rice rods enables the prepared ammonium tungsten bronze hollow microsphere to have good crystallization property and dispersibility, and the particle size distribution of the microsphere is concentrated.
In the present invention, the separation is preferably performed by centrifugation. The present invention is not particularly limited to the specific operation of the centrifugation, and a centrifugation method known to those skilled in the art may be used.
After the centrifugation is completed, the precipitate obtained by the centrifugation is preferably washed and dried in sequence. In the invention, the washing sequence is preferably water washing and absolute ethyl alcohol washing in sequence, the number of times of the water washing is preferably 3-5, and the number of times of the absolute ethyl alcohol washing is preferably 2-3. In the invention, the drying temperature is preferably 50-70 ℃, more preferably 60 ℃, and the time is preferably 8 h.
The invention also provides the ammonium tungsten bronze hollow microsphere prepared by the preparation method in the technical scheme, the ammonium tungsten bronze hollow microsphere takes a mixture of ammonium tungsten bronze nanoparticles and ammonium tungsten bronze nanorods as a shell, and the particle size of the ammonium tungsten bronze nanoparticles in the mixture of the ammonium tungsten bronze nanoparticles and the ammonium tungsten bronze nanorods is 30-160 nm; the length of the ammonium tungsten bronze nanorod is 0.4-1.8 mu m, the diameter of the nanorod is 20-140 nm, and the particle size of the ammonium tungsten bronze hollow microsphere is 4-15 mu m.
The ammonium tungsten bronze hollow microspheres and the preparation method thereof provided by the present invention will be described in detail with reference to the following examples, but they should not be construed as limiting the scope of the present invention.
Example 1
A preparation method of ammonium tungsten bronze hollow microspheres comprises the following steps:
1) adding 1g (4.3mmol) of tungsten trioxide powder and 0.98g (12.9mmol) of thiourea into 40mL of water, fully stirring, dissolving and uniformly mixing to obtain reaction precursor liquid;
2) transferring the reaction precursor solution into a stainless steel reaction kettle, sealing, carrying out hydrothermal reaction for 12 hours at 200 ℃, naturally cooling, and centrifuging, wherein the filling ratio of the stainless steel reaction kettle is 80%;
3) and washing the precipitate obtained by centrifugation with deionized water for 3 times, washing with absolute ethyl alcohol for 2 times, and drying at 60 ℃ for 8 hours to obtain the ammonium tungsten bronze hollow microsphere.
The ammonium tungsten bronze hollow microsphere is a microsphere with the average particle size of 8 mu m, which is composed of nano-particles with the average particle size of 75nm and nano-rods with the average length of 0.9 mu m and the average diameter of 65 nm.
Fig. 1 is an XRD pattern of the ammonium tungsten bronze hollow microsphere prepared in example 1, as shown in fig. 1, the XRD peak position of the prepared ammonium tungsten bronze hollow microsphere is consistent with the standard diffraction pattern, which reflects that the product prepared in example 1 is ammonium tungsten bronze, and the product has good crystallization property and high purity.
FIG. 2 is an SEM image of the ammonium tungsten bronze hollow microsphere prepared in example 1 at 1000 times, FIG. 3 is an SEM image of the ammonium tungsten bronze hollow microsphere prepared in example 1 at 20000 times, and it can be seen from FIGS. 2 to 3 that the ammonium tungsten bronze hollow microsphere is a hollow structure, and is a microsphere with an average particle size of 8 μm, which is composed of nanoparticles with an average particle size of 75nm and nanorods with an average length of 0.9 μm and an average diameter of 65nm, and the microsphere has good dispersibility and concentrated particle size distribution.
Example 2
A preparation method of ammonium tungsten bronze hollow microspheres comprises the following steps:
1) adding 0.95g (4.1mmol) of tungsten trioxide powder and 0.86g (11.3mmol) of thiourea into 40mL of water, fully stirring, dissolving and uniformly mixing to obtain reaction precursor liquid;
2) transferring the reaction precursor solution into a stainless steel reaction kettle, sealing, carrying out hydrothermal reaction for 9 hours at 210 ℃, naturally cooling, and centrifuging, wherein the filling ratio of the stainless steel reaction kettle is 80%;
3) and washing the precipitate obtained by centrifugation with deionized water for 3 times, washing with absolute ethyl alcohol for 2 times, and drying at 60 ℃ for 8 hours to obtain the ammonium tungsten bronze hollow microsphere.
The ammonium tungsten bronze hollow microsphere is a microsphere with the average particle size of 6.5 mu m, which is composed of nano-particles with the average particle size of 65nm and nano-rods with the average length of 0.8 mu m and the average diameter of 50 nm.
Example 3
A preparation method of ammonium tungsten bronze hollow microspheres comprises the following steps:
1) adding 1.05g (4.5mmol) of tungsten trioxide powder and 1.13g (14.8mmol) of thiourea into 40mL of water, fully stirring, dissolving and uniformly mixing to obtain reaction precursor liquid;
2) transferring the reaction precursor solution into a stainless steel reaction kettle, sealing, carrying out hydrothermal reaction for 20 hours at 190 ℃, naturally cooling, and centrifuging, wherein the filling ratio of the stainless steel reaction kettle is 80%;
3) and washing the precipitate obtained by centrifugation with deionized water for 3 times, washing with absolute ethyl alcohol for 2 times, and drying at 60 ℃ for 8 hours to obtain the ammonium tungsten bronze hollow microsphere.
The ammonium tungsten bronze hollow microsphere is a microsphere with the average particle size of 10 mu m, which is composed of nano-particles with the average particle size of 90nm and nano-rods with the average length of 1.1 mu m and the average diameter of 80 nm.
Example 4
The production method of this example is similar to that of example 1, with the specific difference that the molar ratio of tungsten trioxide powder to thiourea was 1: 1.49.
FIG. 4 is an SEM image of the product prepared in example 4 at 100000 times, and it can be seen that the product is porous diamond-like nanoparticles and a small amount of nanorods, and pure phase ammonium tungsten bronze and hollow microsphere structures cannot be obtained.
Example 5
The production method of this example is similar to that of example 1, with the specific difference that the molar ratio of tungsten trioxide powder to thiourea was 1: 5.00.
Fig. 5 is an SEM image of the product prepared in example 5 at 100000 x, from which it can be seen that the product is mainly porous diamond-like nanoparticles, and phase-pure ammonium tungsten bronze and hollow microsphere structures are not obtained.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (4)
1. A preparation method of ammonium tungsten bronze hollow microspheres is characterized by comprising the following steps:
mixing tungsten trioxide, thiourea and water, carrying out hydrothermal reaction, and then sequentially separating and drying to obtain the ammonium tungsten bronze hollow microsphere; the ammonium tungsten bronze hollow microsphere takes a mixture of ammonium tungsten bronze nanoparticles and ammonium tungsten bronze nanorods as a shell, and the particle size of the ammonium tungsten bronze nanoparticles in the mixture of the ammonium tungsten bronze nanoparticles and the ammonium tungsten bronze nanorods is 30-160 nm; the length of the ammonium tungsten bronze nanorod is 0.4-1.8 mu m, and the diameter of the ammonium tungsten bronze nanorod is 20-140 nm; the particle size of the ammonium tungsten bronze hollow microsphere is 4-15 mu m; the molar ratio of the tungsten trioxide to the thiourea is 1 (2.7-3.3); the temperature of the hydrothermal reaction is 190-210 ℃, and the time is 9-20 h.
2. The production method according to claim 1, wherein the molar concentration of the tungsten trioxide in the mixed solution of tungsten trioxide, thiourea and water is 0.08 to 0.14 mol/L.
3. The preparation method according to claim 1, wherein the molar concentration of the thiourea in the mixed solution of tungsten trioxide, thiourea and water is 0.29 to 0.36 mol/L.
4. The preparation method according to claim 1, wherein the drying temperature is 50-70 ℃ and the drying time is 6-10 h.
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