CN116282174A - Preparation method of tungsten oxide nano-micro material in metal ion auxiliary and acid and alkaline environments - Google Patents
Preparation method of tungsten oxide nano-micro material in metal ion auxiliary and acid and alkaline environments Download PDFInfo
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- CN116282174A CN116282174A CN202310381741.8A CN202310381741A CN116282174A CN 116282174 A CN116282174 A CN 116282174A CN 202310381741 A CN202310381741 A CN 202310381741A CN 116282174 A CN116282174 A CN 116282174A
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- QGLKJKCYBOYXKC-UHFFFAOYSA-N nonaoxidotritungsten Chemical compound O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 QGLKJKCYBOYXKC-UHFFFAOYSA-N 0.000 title claims abstract description 58
- 229910001930 tungsten oxide Inorganic materials 0.000 title claims abstract description 58
- 239000000463 material Substances 0.000 title claims abstract description 48
- 229910021645 metal ion Inorganic materials 0.000 title claims abstract description 25
- 239000002253 acid Substances 0.000 title claims abstract description 19
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 238000000034 method Methods 0.000 claims abstract description 22
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims abstract description 12
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 7
- 230000002378 acidificating effect Effects 0.000 claims abstract description 6
- 239000013078 crystal Substances 0.000 claims abstract description 6
- 239000011780 sodium chloride Substances 0.000 claims abstract description 6
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910052721 tungsten Inorganic materials 0.000 claims abstract description 6
- 239000010937 tungsten Substances 0.000 claims abstract description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 6
- 238000001354 calcination Methods 0.000 claims abstract description 4
- 239000002245 particle Substances 0.000 claims abstract description 4
- PBYZMCDFOULPGH-UHFFFAOYSA-N tungstate Chemical compound [O-][W]([O-])(=O)=O PBYZMCDFOULPGH-UHFFFAOYSA-N 0.000 claims abstract description 4
- 230000001105 regulatory effect Effects 0.000 claims abstract description 3
- PHFQLYPOURZARY-UHFFFAOYSA-N chromium trinitrate Chemical compound [Cr+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O PHFQLYPOURZARY-UHFFFAOYSA-N 0.000 claims description 10
- 229910052751 metal Inorganic materials 0.000 claims description 10
- 239000002184 metal Substances 0.000 claims description 10
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 8
- 238000006243 chemical reaction Methods 0.000 claims description 6
- 239000000843 powder Substances 0.000 claims description 6
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 4
- 229910052759 nickel Inorganic materials 0.000 claims description 4
- 239000007787 solid Substances 0.000 claims description 4
- 230000003993 interaction Effects 0.000 claims description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 2
- 229910021555 Chromium Chloride Inorganic materials 0.000 claims description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 2
- 229910002651 NO3 Inorganic materials 0.000 claims description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 2
- 238000010306 acid treatment Methods 0.000 claims description 2
- 229910052804 chromium Inorganic materials 0.000 claims description 2
- 239000011651 chromium Substances 0.000 claims description 2
- QSWDMMVNRMROPK-UHFFFAOYSA-K chromium(3+) trichloride Chemical compound [Cl-].[Cl-].[Cl-].[Cr+3] QSWDMMVNRMROPK-UHFFFAOYSA-K 0.000 claims description 2
- 229910017052 cobalt Inorganic materials 0.000 claims description 2
- 239000010941 cobalt Substances 0.000 claims description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 2
- 229910052802 copper Inorganic materials 0.000 claims description 2
- 239000010949 copper Substances 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims description 2
- 238000000227 grinding Methods 0.000 claims description 2
- 229910052742 iron Inorganic materials 0.000 claims description 2
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims description 2
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 2
- 150000003839 salts Chemical class 0.000 claims description 2
- 239000012265 solid product Substances 0.000 claims description 2
- CMPGARWFYBADJI-UHFFFAOYSA-L tungstic acid Chemical compound O[W](O)(=O)=O CMPGARWFYBADJI-UHFFFAOYSA-L 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims description 2
- 239000011701 zinc Substances 0.000 claims description 2
- 229910052725 zinc Inorganic materials 0.000 claims description 2
- -1 zinc metals Chemical class 0.000 claims 1
- 238000001027 hydrothermal synthesis Methods 0.000 abstract description 6
- 239000003513 alkali Substances 0.000 abstract description 5
- 239000012752 auxiliary agent Substances 0.000 abstract description 5
- 230000001699 photocatalysis Effects 0.000 abstract description 4
- 230000008569 process Effects 0.000 abstract description 4
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 abstract description 3
- 229910001416 lithium ion Inorganic materials 0.000 abstract description 3
- 239000000203 mixture Substances 0.000 abstract description 3
- 238000007146 photocatalysis Methods 0.000 abstract description 3
- 238000011084 recovery Methods 0.000 abstract description 3
- 238000001308 synthesis method Methods 0.000 abstract description 3
- 238000003786 synthesis reaction Methods 0.000 abstract description 3
- 230000003373 anti-fouling effect Effects 0.000 abstract description 2
- 238000005272 metallurgy Methods 0.000 abstract description 2
- 238000002156 mixing Methods 0.000 abstract description 2
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical class [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 abstract 1
- 239000007864 aqueous solution Substances 0.000 abstract 1
- 230000009286 beneficial effect Effects 0.000 abstract 1
- 230000005540 biological transmission Effects 0.000 abstract 1
- 239000000376 reactant Substances 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 13
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 8
- ZNOKGRXACCSDPY-UHFFFAOYSA-N tungsten trioxide Chemical compound O=[W](=O)=O ZNOKGRXACCSDPY-UHFFFAOYSA-N 0.000 description 8
- 239000007789 gas Substances 0.000 description 6
- 239000012071 phase Substances 0.000 description 5
- XMVONEAAOPAGAO-UHFFFAOYSA-N sodium tungstate Chemical compound [Na+].[Na+].[O-][W]([O-])(=O)=O XMVONEAAOPAGAO-UHFFFAOYSA-N 0.000 description 5
- 239000000047 product Substances 0.000 description 4
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- 230000007935 neutral effect Effects 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- 239000000543 intermediate Substances 0.000 description 2
- 230000035945 sensitivity Effects 0.000 description 2
- BCKXLBQYZLBQEK-KVVVOXFISA-M Sodium oleate Chemical compound [Na+].CCCCCCCC\C=C/CCCCCCCC([O-])=O BCKXLBQYZLBQEK-KVVVOXFISA-M 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 239000011365 complex material Substances 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 239000004005 microsphere Substances 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 239000011941 photocatalyst Substances 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 238000011112 process operation Methods 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000000638 solvent extraction Methods 0.000 description 1
- 238000004729 solvothermal method Methods 0.000 description 1
- 239000011232 storage material Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000011282 treatment Methods 0.000 description 1
- 238000010977 unit operation Methods 0.000 description 1
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Classifications
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G41/00—Compounds of tungsten
- C01G41/02—Oxides; Hydroxides
-
- C—CHEMISTRY; METALLURGY
- 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
-
- C—CHEMISTRY; METALLURGY
- 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
-
- C—CHEMISTRY; METALLURGY
- 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
- C01P2004/62—Submicrometer sized, i.e. from 0.1-1 micrometer
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
The invention relates to a preparation method of a tungsten oxide nano-micro material in an acid and alkali environment with the assistance of metal ions. The tungsten oxide nano-micro material with spherical granularity of 200-3000nm is obtained by taking tungstate as a reactant, mixing with a certain amount of sodium chloride and metal salt auxiliary agent, dissolving in water, regulating the pH value of an aqueous solution system to 0.5-9.0, reacting for 2-48 hours at 160-220 ℃ in a hydrothermal reaction kettle, and calcining for 1-3 hours at 300-900 ℃. Unlike conventional synthesis methods, the method of the invention has the advantage of simultaneously realizing high-yield synthesis of the tungsten oxide nano-micro material in an acidic or alkaline environment; particularly, tungsten oxide materials which cannot be obtained under the alkaline condition without the assistance of metal ions can be prepared, the use of acid is avoided, the preparation process is safe and simple, and the synthesis under the alkaline condition provides practical guiding significance for solving the problem of high difficulty of alkali recovery in the tungsten metallurgy process; the synthesized tungsten oxide has the advantages of good crystallinity, high yield, uniform particles, stable crystal structure and strong electron transmission capability. The invention can provide the tungsten oxide nano-micro material with adjustable structure and composition and uniform granularity, and is beneficial to expanding the practical application of the material in the fields of photo/electrochromic devices, lithium ion batteries, gas sensors, photocatalysis, antifouling and the like.
Description
Technical Field
The invention belongs to the technical field of nano-micro material preparation, and relates to a method for preparing a tungsten oxide nano-micro material.
Background
Tungsten oxide is an ecologically friendly, inexpensive, abundant and readily available material, and is of great interest due to its particular nature and the wide range of modification means. Tungsten oxide is an n-type semiconductor material, has a proper band gap, can absorb visible light in a large range, and becomes one of the most potential photocatalysts. The tungsten oxide has excellent gas sensitivity by absorbing various gases. Tungsten oxide has the ability to intercalate lithium ions, a property that makes it both an energy storage material and an electrochromic material. In addition, tungsten oxide has the advantages of chemical stability, photo-corrosion resistance, biocompatibility, adjustable band gap, excellent hole mobility and the like. Therefore, the tungsten oxide has important application value in the fields of photo/electrochromic devices, lithium ion batteries, gas sensors, photocatalysis, antifouling and the like.
Tungsten oxide is a highly complex material from a crystal structure point of view. Different synthetic routes and post-treatments can influence the morphology, crystalline phase and defect structure of the obtained tungsten oxide, thereby influencing the intrinsic properties of the material and the application thereof. The tungsten oxide synthesis method is usually a liquid phase synthesis method, is simple and easy to modulate, and comprises a hydrothermal method and a solvothermal method. Among them, the hydrothermal method is most widely used, mainly using tungstate as tungsten source, controlling pH range between 1 and 2, and forming tungsten oxide by hydrothermal decomposition. For example, sun et al use sodium tungstate as the tungsten source, sodium oleate as the structure directing agent, and hydrothermal at 180 ℃ at pH 1 to produce tungsten trioxide nano-microtubes (s.sun, et al Journal oftheAmericanChemicalSociety,2018,140 (20), 6474-6482); zhang et al achieved an orthorhombic tungsten trioxide hierarchical structure (y.zhang, et al, materials letters,2019,235,49-52) by adding cetyl trimethylammonium bromide (CTAB) surfactant to assist hydrothermal synthesis at a pH of 1-1.5; liu et al prepared tungsten trioxide nano-micro hollow microspheres by dissolving sodium tungstate and oxalic acid in a mixed solution of isopropanol and hydrochloric acid (Y. Liu, et al, crystal engineering communication,2014,16,7493-7501). It has been reported that hydrothermal synthesis is mostly performed in an environment with pH less than 2, requires a relatively large amount of strong acid to be consumed for adjustment, and tungsten oxide cannot be formed under alkaline conditions by the previously reported methods. The synthesis of tungsten oxide by metal ion induction under the weak acidic or alkaline condition of high pH is not reported, and is still blank.
The invention provides a method for synthesizing a tungsten oxide nano-micro material in an acid and alkaline environment with the assistance of metal ions, and the process is simple and controllable. The tungsten oxide material synthesized by the method has the characteristics of high purity, good dispersity, high crystallinity, uniform size and the like, shows good photocatalytic activity and gas-sensitive performance, and has wide application prospect. In the prior art, the problem of difficult alkali recovery exists in the tungsten metallurgy process, and in order to realize alkali recovery, a plurality of unit operations such as solution conversion, solvent extraction, ion exchange, evaporative crystallization and the like are needed in the process operation, and the method provided by the invention has substantial guiding significance for the process of directly precipitating tungsten trioxide or the hydrate thereof to recover alkali.
Disclosure of Invention
The invention provides a preparation method of a tungsten oxide nano-micro material, which is simple and easy to implement, and can regulate and synthesize a series of tungsten oxide nano-micro materials with different crystal structures, different morphologies, different sizes and different compositions.
The preparation method provided by the invention adopts the following technical scheme:
the preparation method of the tungsten oxide nano-micro material in the acid and alkaline environment assisted by metal ions is characterized by comprising the following steps:
dissolving tungstate and sodium chloride in water, adding a certain amount of metal salt, regulating the pH value with a small amount of acid to make the solution acidic or alkaline, uniformly mixing, transferring into a high-pressure reaction kettle, reacting for 2-48 hours at 160-220 ℃, washing, drying and grinding the formed solid product into fine powder, and calcining for 1-3 hours at 300-900 ℃ to obtain solid powder, namely the tungsten oxide nano-micro material. The preparation method mainly has the following characteristics:
the introduction of the metal ion auxiliary agent is a key condition that the tungsten oxide nano-micro material can be formed in an alkaline environment.
In an acidic environment, the interaction between the metal ion auxiliary agent and the tungstic acid intermediate can regulate and control the formation and structure of the tungsten oxide nano-micro material.
The pH value of the reaction liquid before hydrothermal reaction is in the range of 0.5-9.0.
The metal ion auxiliary agent is one or more of nitrate, acetate or chloride of chromium, manganese, nickel, iron, cobalt, nickel, copper or zinc metal, such as chromium nitrate, nickel nitrate, chromium chloride and the like.
The amount of the metal ion auxiliary agent added accounts for 0.5-15% of the mole percentage of the tungsten element added.
The particle size of the prepared tungsten oxide nano-micro material is 200-3000nm.
The tungsten oxide is a crystal structure material comprising cubic phase, monoclinic phase, hexagonal phase and mixed phase thereof.
The prepared solid powder product is a tungsten oxide nano-micro material containing trace doped metal or a tungsten oxide nano-micro material which is obtained by acid treatment and has no doped metal and metal vacancy.
Different from other preparation methods, the method provided by the invention is to regulate and control the formation of tungsten oxide through the interaction of metal ions and tungstate radical intermediates, and realize the formation of tungsten oxide in alkaline environment and the improvement of uniformity of tungsten oxide particles in acidic condition. The tungsten oxide material prepared by the method has good performances of photocatalysis, gas sensitivity and the like, is easy to modulate in composition, structure and performance, and has wider market application value.
Description of the drawings:
FIG. 1 is an SEM image of a tungsten oxide material produced in accordance with an example of the present invention;
FIG. 2 is a comparison of the gas-sensitive properties of tungsten oxide materials prepared in accordance with examples of the present invention to acetone.
Detailed Description
The present invention will be further illustrated with reference to the following examples, but the present invention is not limited to the following examples.
Example 1
6.6000g of sodium tungstate is dissolved in 30ml of water, 5.8500g of sodium chloride is added, hydrochloric acid is used for adjusting the solution to be neutral after the solution is clear and transparent, 0.4637g of chromium nitrate is added, the pH is adjusted to 3.5, the solution is stirred for 1 hour, the solution is transferred into a polytetrafluoroethylene-lined high-pressure reaction kettle, the temperature is kept constant for 24 hours at 180 ℃, and the product is centrifuged, washed, dried and ground at 60 ℃ and calcined in a muffle furnace at 300 ℃ for 2 hours to obtain the tungsten oxide material.
Example 2
6.6000g of sodium tungstate is dissolved in 30ml of water, 5.8500g of sodium chloride is added, hydrochloric acid is used for adjusting the solution to be neutral after the solution is clear and transparent, 0.2319g of chromium nitrate is added, the pH is adjusted to 4.5, the solution is stirred for 2 hours, the solution is transferred into a polytetrafluoroethylene-lined high-pressure reaction kettle, the temperature is kept at 180 ℃ for 18 hours, and the product is centrifuged, washed, dried at 60 ℃ and ground and calcined in a muffle furnace at 300 ℃ for 2 hours to obtain the tungsten oxide material.
Example 3
6.6000g of sodium tungstate is dissolved in 30ml of water, 5.8500g of sodium chloride is added, hydrochloric acid is used for adjusting the solution to be neutral after the solution is clear and transparent, 0.4637g of chromium nitrate is added, the solution is stirred for 1 hour and then is transferred into a polytetrafluoroethylene-lined high-pressure reaction kettle, the temperature is kept constant for 24 hours at 180 ℃, and the product is centrifuged, washed, dried and ground at 60 ℃ and calcined in a muffle furnace at 300 ℃ for 1 hour to obtain the tungsten oxide material.
Claims (9)
1. The preparation method of the tungsten oxide nano-micro material in the acid and alkaline environment assisted by metal ions is characterized by comprising the following steps: dissolving tungstate and sodium chloride in water, adding a certain amount of metal salt, regulating the pH value with a small amount of acid to make the solution acidic or alkaline, transferring into a high-pressure reaction kettle, reacting for 2-48 hours at 160-220 ℃, washing, drying and grinding the formed solid product into fine powder, and calcining for 1-3 hours at 300-900 ℃ to obtain solid powder, namely the tungsten oxide nano-micro material.
2. The method for preparing the tungsten oxide nano-micro material in the alkaline environment and the acid-alkaline environment, which is characterized in that the metal ion assistance is introduced in the alkaline environment, which is a necessary condition for forming the tungsten oxide nano-micro material.
3. The method for preparing the tungsten oxide nano-micro material in an acid and alkaline environment with the assistance of metal ions according to claim 1, wherein the interaction of the metal ions and the tungstic acid intermediate in the acid environment promotes the formation of uniform tungsten oxide nano-micro structures.
4. The method for preparing the tungsten oxide nano-micro material in the metal ion auxiliary and acid and alkaline environment according to claim 1, wherein the pH value of the acid or alkaline system is in the range of 0.5-9.0.
5. The method for preparing the tungsten oxide nano-micro material in the acid and alkaline environment, which is assisted by metal ions according to claim 1, wherein the metal ions involved in the metal ion assistance comprise one or more of nitrate, acetate or chloride of chromium, manganese, nickel, iron, cobalt, nickel, copper or zinc metals, such as chromium nitrate, nickel nitrate, chromium chloride and the like.
6. The method for preparing the tungsten oxide nano-micro material in the acid and alkaline environment with the assistance of metal ions according to claim 1, wherein the added metal ions account for 0.5-15 mol percent of tungsten element.
7. The method for preparing the tungsten oxide nano-micro material in the acid and alkaline environment with the assistance of metal ions according to claim 1, wherein the tungsten oxide nano-micro material prepared by the method has the particle size of 200-3000nm.
8. The method for preparing the tungsten oxide nano-micro material in the acid and alkaline environment with the assistance of metal ions according to claim 1, wherein the tungsten oxide prepared by the method comprises cubic phase, monoclinic phase, hexagonal phase and mixed phase crystal structure materials thereof.
9. The method for preparing the tungsten oxide nano-micro material in the acid and alkaline environment with the assistance of metal ions according to claim 1, wherein the solid powder obtained after calcination is the tungsten oxide nano-micro material containing trace doped metal or the tungsten oxide nano-micro material which is obtained after acid treatment and has no doped metal and metal vacancy.
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2023
- 2023-04-11 CN CN202310381741.8A patent/CN116282174A/en active Pending
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