CN111072067B - A kind of ammonium tungsten bronze hollow microsphere and preparation method thereof - Google Patents
A kind of ammonium tungsten bronze hollow microsphere and preparation method thereof Download PDFInfo
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- CN111072067B CN111072067B CN201911379090.9A CN201911379090A CN111072067B CN 111072067 B CN111072067 B CN 111072067B CN 201911379090 A CN201911379090 A CN 201911379090A CN 111072067 B CN111072067 B CN 111072067B
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- 229910000906 Bronze Inorganic materials 0.000 title claims abstract description 95
- ZGRBQKWGELDHSV-UHFFFAOYSA-N N.[W+4] Chemical compound N.[W+4] ZGRBQKWGELDHSV-UHFFFAOYSA-N 0.000 title claims abstract description 95
- 239000010974 bronze Substances 0.000 title claims abstract description 95
- KUNSUQLRTQLHQQ-UHFFFAOYSA-N copper tin Chemical compound [Cu].[Sn] KUNSUQLRTQLHQQ-UHFFFAOYSA-N 0.000 title claims abstract description 94
- 239000004005 microsphere Substances 0.000 title claims abstract description 57
- 238000002360 preparation method Methods 0.000 title claims abstract description 27
- ZNOKGRXACCSDPY-UHFFFAOYSA-N tungsten trioxide Chemical compound O=[W](=O)=O ZNOKGRXACCSDPY-UHFFFAOYSA-N 0.000 claims abstract description 58
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims abstract description 55
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 27
- 239000002245 particle Substances 0.000 claims abstract description 23
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 21
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 20
- 229910001868 water Inorganic materials 0.000 claims abstract description 18
- 238000001035 drying Methods 0.000 claims abstract description 12
- 239000002105 nanoparticle Substances 0.000 claims description 25
- 239000002073 nanorod Substances 0.000 claims description 24
- 239000011259 mixed solution Substances 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- 238000000926 separation method Methods 0.000 claims description 2
- 238000002156 mixing Methods 0.000 abstract description 7
- 238000009826 distribution Methods 0.000 abstract description 5
- 239000002994 raw material Substances 0.000 abstract description 3
- 229910010272 inorganic material Inorganic materials 0.000 abstract description 2
- 239000011147 inorganic material Substances 0.000 abstract description 2
- 238000006243 chemical reaction Methods 0.000 description 20
- 239000000047 product Substances 0.000 description 11
- 238000005406 washing Methods 0.000 description 11
- 238000005119 centrifugation Methods 0.000 description 8
- 229910001220 stainless steel Inorganic materials 0.000 description 8
- 239000010935 stainless steel Substances 0.000 description 8
- 238000001878 scanning electron micrograph Methods 0.000 description 7
- 239000002243 precursor Substances 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- 238000002425 crystallisation Methods 0.000 description 5
- 230000008025 crystallization Effects 0.000 description 5
- 229910000069 nitrogen hydride Inorganic materials 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- XAYGUHUYDMLJJV-UHFFFAOYSA-Z decaazanium;dioxido(dioxo)tungsten;hydron;trioxotungsten Chemical compound [H+].[H+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O XAYGUHUYDMLJJV-UHFFFAOYSA-Z 0.000 description 4
- 238000011049 filling Methods 0.000 description 4
- 239000002244 precipitate Substances 0.000 description 4
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 3
- 230000002776 aggregation Effects 0.000 description 3
- 235000011114 ammonium hydroxide Nutrition 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 238000006460 hydrolysis reaction Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 238000007789 sealing Methods 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- -1 tungsten bronze compound Chemical class 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 238000004220 aggregation Methods 0.000 description 2
- 239000011258 core-shell material Substances 0.000 description 2
- 238000005034 decoration Methods 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000011031 large-scale manufacturing process Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000010899 nucleation Methods 0.000 description 2
- 230000006911 nucleation Effects 0.000 description 2
- 239000007790 solid phase Substances 0.000 description 2
- 238000004729 solvothermal method Methods 0.000 description 2
- 238000005979 thermal decomposition reaction Methods 0.000 description 2
- 239000010937 tungsten Substances 0.000 description 2
- 229910052721 tungsten Inorganic materials 0.000 description 2
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- 230000002687 intercalation Effects 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 239000002159 nanocrystal Substances 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
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- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G41/00—Compounds of tungsten
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
- B01J13/02—Making microcapsules or microballoons
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
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- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
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- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/10—Particle morphology extending in one dimension, e.g. needle-like
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- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/10—Particle morphology extending in one dimension, e.g. needle-like
- C01P2004/16—Nanowires or nanorods, i.e. solid nanofibres with two nearly equal dimensions between 1-100 nanometer
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- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/30—Particle morphology extending in three dimensions
- C01P2004/32—Spheres
- C01P2004/34—Spheres hollow
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- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
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- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/62—Submicrometer sized, i.e. from 0.1-1 micrometer
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- C01P2004/64—Nanometer sized, i.e. from 1-100 nanometer
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Abstract
本发明提供了一种铵钨青铜中空微球及其制备方法，属于无机材料的制备技术领域。本发明提供的制备方法，包括以下步骤：将三氧化钨、硫脲和水混合，进行水热反应后，依次进行分离和干燥，得到铵钨青铜中空微球。本发明以三氧化钨和硫脲为原料，采用水热法制备了铵钨青铜中空微球，使制得的铵钨青铜中空微球纯度高，结晶性能和分散性好，粒径分布集中。
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 present invention comprises the following steps: mixing tungsten trioxide, thiourea and water, performing a hydrothermal reaction, then separating and drying in sequence to obtain ammonium tungsten bronze hollow microspheres. The invention uses tungsten trioxide and thiourea as raw materials, and adopts a hydrothermal method to prepare ammonium tungsten bronze hollow microspheres, so that the prepared ammonium tungsten bronze hollow microspheres have high purity, good crystallinity 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)
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