CN101381106A - Method for preparing nano tungsten trioxide powder - Google Patents
Method for preparing nano tungsten trioxide powder Download PDFInfo
- Publication number
- CN101381106A CN101381106A CNA2007100499429A CN200710049942A CN101381106A CN 101381106 A CN101381106 A CN 101381106A CN A2007100499429 A CNA2007100499429 A CN A2007100499429A CN 200710049942 A CN200710049942 A CN 200710049942A CN 101381106 A CN101381106 A CN 101381106A
- Authority
- CN
- China
- Prior art keywords
- gel
- powder
- acid
- nanometer
- tungsten trioxide
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Abstract
The invention discloses a method for preparing nanometer tungstic oxide nanopowder. The method for producing the high-quality nanometer WO3 powder with high efficiency comprises the following steps: according to the rate of 1 to 1, 13.4 to15mol/L of ammonia and deionized water are prepared into the needed ammonia solution; tungstenic acid is dissolved into the prepared ammonia solution; citric acid which has the molar ratio with the tungstenic acid by 2 to 4 times is added into the solution, is heated at the temperature of between 80 and 90 DEG C and is stirred for 8 to 12 hours to obtain a yellowish transparent gel; the prepared gel is positioned in an infrared oven for roasting till brown expanded gel is obtained; and the gel obtained by the steps is calcined in a chamber furnace at the temperature of between 550 and 650 DEG C to obtain yellow nanometer tungstic oxide powder. Compared with the prior art, the method has the advantages of simple and feasible process,, less environmental pollution, less erosion to equipment and relatively low production cost.
Description
Technical field
The invention belongs to the tungsten trioxide powder preparing technical field, a kind of nano tungsten trioxide (WO particularly is provided
3) preparation method of powder, realized the high-quality and efficient production of nano tungsten trioxide.
Background technology
Nanometer WO
3Powder is a kind of important industrial raw material, can be used to prepare nano-tungsten powder and nano powder of tungsten carbide, in addition nanometer WO
3Hertzian wave there is very strong receptivity, in the utilization of sun power, can be used as the excellent absorption material, militarily can make important stealth material, nanometer WO
3Have huge specific surface area, surface effects is remarkable, makes a kind of good catalyzer; As the compound of transition metal, nanometer WO
3Also having characteristic of semiconductor, is a kind of very potential sensitive material, to H
2S, NH
3Has susceptibility etc. multiple gases.
Present common preparation WO
3Method have solid phase method, liquid phase method and vapor phase process following several:
1) solid reaction process
Be a kind of traditional powdered technology, comprise that mainly para-tungstic acid is by (APT), wolframic acid (H
2WO
4), wolframic acid ammonia ((NH
4)
6W
7O
246H
2O) calcining is three kinds, and solid phase method is simple, is to produce conventional WO
3The commercial run of powder, but it easily produces toxic gas in decomposition course, cause environmental pollution, and the nanometer WO that produces
3Distributed more widely and the easy reunion of powder granularity needs secondary to pulverize, and cost is higher.
2) liquid phase method comprises that sol-gel method, chemical precipitation method, microemulsion method and hydrothermal synthesis method are several.
2.1 sol-gel method
Sol-gel method is with inorganic salt or metal alkoxide hydrolysis, make solute party gelation then, perhaps in the aqueous solution of metal inorganic salt, add a certain amount of organic acid and make part, pH value with the inorganic acid alkali regulation system, slowly evaporation obtains gel, again with gel drying, accompany burning, obtain the method for nano-powder.Main (the NH that utilizes
4)
10W
12O
415H
2O is a presoma, adds a certain proportion of pure and mild ester class, forms gel through behind the certain hour, and drying and calcining makes nanometer anhydrous wolframic acid powder again.
This method can make the less nanometer trioxide powder of particle, but the transformation of control sol-gel is difficult, the hard aggregation phenomenon that is easy to get after the product oven dry, and the production cycle is long, is not suitable for scale operation.
2.2 chemical precipitation method
Chemical precipitation method is to add suitable precipitation agent to obtain the ceramic forerunner throw out in metal salt solution, again throw out dehydration, calcining is formed nano-ceramic powder.Precipitation legal system WO
3Powder utilizes this principle exactly.With Na
2WO
4, (NH
4)
10W
12O
415H
2O is a raw material, adds suitable acid and makes wolframic acid, again the wolframic acid calcining is obtained WO
3Powder.
Chemical precipitation method can access the nanometer anhydrous wolframic acid powder body, but Na
2WO
4For raw material is introduced impurity Na easily, and be difficult for deviating from; (NH
4)
10W
12O
415H
2The water solubility of O is little, and reaction efficiency is low, easily causes the wasting of resources.
The wet chemical method of Chu Xianing is to obtain (NH with wolframic acid and ammoniacal liquor reaction on this basis
4)
10W
12O
415H
2O replaces Na
2WO
4, regulate pH value with dilute hydrochloric acid again, obtain wolframic acid through the overaging precipitation, calcining and decomposing obtains nanometer WO
3Powder.The shortcoming of this method is that productive rate is low, and reaction time is long, and efficient is low.
The coprecipitation method that develops on this basis is the method that preparation contains the composite oxides super-fine powder of two or more metallic elements.At WCl
6And TiCl
4The aqueous solution in add ammoniacal liquor and suitable tensio-active agent, make it to form W (OH)
6And Ti (OH)
4, centrifugation with this throw out calcining, obtains the nanometer anhydrous wolframic acid powder body again.The shortcoming of this method is to obtain single tungstic oxide powder.
2.3 microemulsion method
The thermodynamic stable system transparent, isotropic that microemulsion method is made up of tensio-active agent, cosurfactant, oil and water usually by the exchange of substance of microemulsion, makes the chemical reaction that carries out in small " pond " be called possibility.The unimolecular layer interface of being formed by tensio-active agent and cosurfactant surrounds and forms the micro emulsion particle, and controlled amount is in a few to tens of nanometers.Utilize (NH
4)
2WO
4Solution is added in the emulsion that contains tensio-active agent, after the excusing from death emulsification, adds strong acid, and reflection generates precipitation, and centrifugation post precipitation solvent wash makes anhydrous wolframic acid powder after drying.
The tensio-active agent cost of this method is higher, and the reaction process complexity, is unsuitable for extensive powder process.
2.4 hydrothermal synthesis method
Hydrothermal synthesis method is meant and makes inorganic under high temperature, hyperbaric environment or organic compound and hydrate, by control to acceleration dialysis reaction and physical process, the inorganics that is improved again by filtration, washing, drying, thereby obtains ultra-fine, high-purity all kinds of particles.
2.5 spray pyrolysis
Earlier raw material is made into the solution of water, ethanol or other solvents, again by spraying plant with reaction solution atomizing and import in the reactor, solvent is volatilized rapidly, reactant takes place to decompose or burning or other chemical reactions takes place simultaneously, generates and the initial diverse product with brand-new chemical constitution of thing.
Generally be that wolframic acid is dissolved in the ammoniated alkaline aqueous solution by a certain percentage, adopt excusing from death spraying conversion, vacuum-drying to obtain nanometer trioxide powder.The advantage of this method is that preparation cycle is short, but also continuous production can be once finished in reaction, helps industrialization.Shortcoming is to invest greatlyyer, and device parameter adjustment control is strict, and decomposes the gas that produces in the reaction process and have corrodibility, can the direct life-span that influences equipment.
3) vapor phase process
Vapor phase process is directly to utilize gas or by various means material is become gas, makes it to issue biological reason at gaseous phase and changes or chemical transformation, and condensing in process of cooling at last grows up forms the method for nanoparticle.Generally be under air atmosphere, the air pressure of control vapo(u)rization system heats tungsten filament, W and O between 133.3～1199.9P
2Reaction makes WO
3Nano particle.This method is higher to equipment requirements, and investment is big, and reaction process is wayward.
In addition, Chinese patent 200410090645 discloses a kind of preparation method of nanometer anhydrous wolframic acid powder.It is raw material that this method adopts industrial wolframic acid ammonia, add 5%～90% the ammonium salt be equivalent to the wolframic acid quality, add the strong acid (comprising hydrochloric acid, nitric acid or chloroazotic acid) that is equivalent to ammonium tungstate quality 10%～90% again, agitation as appropriate obtains xanchromatic wolframic acid gel rapidly.The wolframic acid gel as in the agitator drier, is forged under 100 ℃～500 ℃ temperature and fried 1～4 hour, make nano tungsten trioxide powder.The shortcoming of this method is:
1, ammonium salt easily decomposes, and ammonium salt decomposes in the heat-processed, easily produces NH
3, SO
2Deng toxic gas, environment is polluted, the strong acid that can damage simultaneously in equipment 2, the reaction process all is volatile acid, and environmental unit is had pollution, and is very big to human body harm.3, the pH value of reaction process is wayward, and it is had relatively high expectations.4, making the wolframic acid gel will clean, otherwise easily introduces impurity.
Summary of the invention
In view of the above shortcoming of prior art, the objective of the invention is to study a kind of new process for preparing nano tungsten trioxide powder, make it to have simple for process, environmental pollution is little, and is little to equipment corrosion, the advantage that production cost is low relatively.The object of the present invention is achieved like this:
The method for preparing nano tungsten trioxide powder, high-quality and efficient production nanometer WO
3Powder comprises following step: ammoniacal liquor (13.4mol/L～15mom/L) be made into required ammonia soln with deionized water with 1:1.Wolframic acid is dissolved in the ammonia soln for preparing, more a certain amount of citric acid is added in the solution, the mol ratio of institute's adding citric acid and wolframic acid is controlled between 2～4:1, in 80 ℃～90 ℃ heated and stirred 8～12 hours, obtains the transparent colloidal sol of little Huang.With prepared gel as for toasting in the IR bake, up to obtaining the brown expanded gel; Gel 550 ℃～650 ℃ calcinings in box-type furnace that above step is obtained obtain the Yellow nanometer tungsten trioxide powder.
Embodiment
Raw materials used equal operational analysis is pure.
Embodiment 1,
(1) preparation of raw material:
Ammoniacal liquor (13.4mol/L) is made into required ammonia soln with deionized water with 1:1.
(2) preparation colloidal sol:
Wolframic acid 4.9972g (0.02mol) is dissolved in the ammonia soln that 72ml prepares, with the wolframic acid mol ratio is that the citric acid (8.416g) of 2:1 joins in the dissolved wolframic acid solution, on the magnetic force heating stirrer, stirred 8～12 hours in 85 ℃ of heating in water bath, obtain the transparent colloidal sol of little Huang.
(3) gel drying is handled:
Prepared gel as for dry in the IR bake, is obtained the brown expanded gel.
(4) calcining obtains tungsten trioxide powder:
Gel as in the corundum crucible, was calcined about two hours for 550 ℃ in box-type furnace, obtained the Yellow nanometer tungsten trioxide powder.The nano particle of gained is spherical, and particle diameter is between 30～50nm.
Embodiment 2,
(1) preparation of raw material:
Ammoniacal liquor (14mol/L) is made into required ammonia soln with deionized water with 1:1.
(2) preparation colloidal sol:
Wolframic acid 4.9972g (0.02mol) is dissolved in the ammonia soln that 72ml prepares, with the wolframic acid mol ratio is that the citric acid (16.832g) of 4:1 joins in the dissolved wolframic acid solution, on the magnetic force heating stirrer, stirred 8～12 hours in 85 ℃ of heating in water bath, obtain the transparent colloidal sol of little Huang.
(3) gel drying is handled:
Prepared gel as for dry in the IR bake, is obtained the brown expanded gel.
(4) calcining obtains tungsten trioxide powder:
Gel as in the corundum crucible, was calcined about two hours for 550 ℃ in box-type furnace, obtained the Yellow nanometer tungsten trioxide powder.The nano particle of gained is spherical, and particle diameter is between 20～40nm, and even particle distribution.
Embodiment 3,
(1) preparation of raw material:
Ammoniacal liquor (14mol/L) is made into required ammonia soln with deionized water with 1:1.
(2) preparation colloidal sol:
Wolframic acid 4.9972g (0.02mol) is dissolved in the ammonia soln that 72ml prepares, with the ratio of wolframic acid mole is that the citric acid (16.832g) of 4:1 joins in the dissolved wolframic acid solution, on the magnetic force heating stirrer, stirred 8～12 hours in 85 ℃ of heating in water bath, obtain the transparent colloidal sol of little Huang.
(3) gel drying is handled:
Prepared gel as for dry in the IR bake, is obtained the brown expanded gel.
(4) calcining obtains tungsten trioxide powder:
Gel as in the corundum crucible, was calcined about two hours for 650 ℃ in box-type furnace, obtained the Yellow nanometer tungsten trioxide powder.The nano particle of gained is spherical, and particle diameter is between 40～60nm, and even particle distribution.
From assistant experiment, to join ammonia soln and just can reach basic effect of the present invention as long as wolframic acid can be dissolved in institute, the upper limit of wolframic acid add-on only depends on that wolframic acid joins the solubleness in the ammonia soln when this temperature; But the ratio of citric acid and wolframic acid but must be 2～4:1; Calcining temperature is lower than 550 degree, can decompose not exclusively; Being higher than 650 degree can make powder size increase.
Advantage main manifestations of the present invention is:
1) the inventive method is at first used ammoniacal liquor (NH3·H
2O) with wolframic acid (H2WO
4) reaction generation (NH4)
2WO
4, adding again citric acid, citric acid slowly ionization goes out H+, with (NH4)
2WO
4Reaction slowly generates H2WO
4, the NH that simultaneously citric acid and ionization goes out4 +, generate macromolecular scaffold, the wolframic acid molecule to be kept apart, at last calcining generates particle diameter at the WO of nanometer scale3。
2) the inventive method prepares WO3Powder, course of reaction be to pH value, ion Concentration does not have harsh requirement, and is simple and easy to control.
3) equipment of reaction needed is simple, and raw material is less, reduces cost.In the middle of the reaction and decompose to produce be nontoxic gas and no corrosive deposit, environmentally safe, harmless to equipment.
Claims (2)
1, a kind of method for preparing nano tungsten trioxide powder, high-quality and efficient production nanometer WO
3Powder is characterized in that, comprises following step: 13.4mol/L～15mol/L ammoniacal liquor and deionized water are made into required ammonia soln with 1:1, wolframic acid are dissolved in the ammonia soln for preparing; A certain amount of citric acid is added in the solution, the mol ratio of institute's adding citric acid and wolframic acid is controlled between 2～4:1 again; In 80 ℃～90 ℃ heated and stirred 8～12 hours, obtain the transparent colloidal sol of little Huang; With prepared gel as for toasting in the IR bake, up to obtaining the brown expanded gel; The gel that above step is obtained is calcined in box-type furnace and is obtained the Yellow nanometer tungsten trioxide powder.
2, the method that prepare nano tungsten trioxide powder according to claim 1 is characterized in that calcining temperature is 550 ℃～650 ℃.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2007100499429A CN101381106B (en) | 2007-09-05 | 2007-09-05 | Method for preparing nano tungsten trioxide powder |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2007100499429A CN101381106B (en) | 2007-09-05 | 2007-09-05 | Method for preparing nano tungsten trioxide powder |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101381106A true CN101381106A (en) | 2009-03-11 |
| CN101381106B CN101381106B (en) | 2011-05-11 |
Family
ID=40461191
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2007100499429A Expired - Fee Related CN101381106B (en) | 2007-09-05 | 2007-09-05 | Method for preparing nano tungsten trioxide powder |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101381106B (en) |
Cited By (21)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102050493A (en) * | 2011-01-14 | 2011-05-11 | 中国科学院上海技术物理研究所 | Method for preparing WO3 nanocrystalline |
| CN102190299A (en) * | 2010-03-18 | 2011-09-21 | 中国科学院上海硅酸盐研究所 | Preparation method of tungsten carbide nanopowder |
| CN102211789A (en) * | 2010-04-08 | 2011-10-12 | 中国科学院合肥物质科学研究院 | Method for preparing tungsten trioxide nano material |
| CN102603007A (en) * | 2012-03-15 | 2012-07-25 | 合肥学院 | Preparation method of tungsten oxide nano powder and metal tungsten nano powder |
| CN102963932A (en) * | 2012-11-13 | 2013-03-13 | 江西稀有金属钨业控股集团有限公司 | Method for preparing ultrafine molybdenum trioxide |
| CN103265081A (en) * | 2013-05-27 | 2013-08-28 | 合肥工业大学 | Method for preparing tungsten oxide nano single crystal by sol-gel method |
| CN103273544A (en) * | 2013-05-27 | 2013-09-04 | 安吉汉洲竹制品有限公司 | Nanometer tungsten oxide photocatalyst paper-base bamboo curtain manufacturing method and product thereof |
| CN103302310A (en) * | 2013-06-24 | 2013-09-18 | 刘亚静 | Tungsten nanopowder |
| CN103302300A (en) * | 2013-06-24 | 2013-09-18 | 刘亚静 | Preparation method of tungsten nano powder |
| CN103303979A (en) * | 2013-06-24 | 2013-09-18 | 刘亚静 | Tungsten oxide (WO3) nanopowder prepared by pyrolysing method |
| CN103303978A (en) * | 2013-06-24 | 2013-09-18 | 刘亚静 | Preparation method of tungsten oxide (WO3) nanometer powder |
| CN103624269A (en) * | 2013-11-29 | 2014-03-12 | 北京航空航天大学 | Nanometer tungsten powder and method for preparing nanometer tungsten powder by adoption of sol-gel hydrogen reduction method |
| CN107381644A (en) * | 2017-08-22 | 2017-11-24 | 西安理工大学 | A kind of preparation method of one-dimensional tungsten trioxide nanowires |
| CN109100343A (en) * | 2018-07-02 | 2018-12-28 | 中国科学院合肥物质科学研究院 | The preparation method of tungsten oxide film |
| CN109987634A (en) * | 2017-12-30 | 2019-07-09 | 卢斌 | A kind of WO3The preparation method of aeroge |
| CN111613820A (en) * | 2020-05-08 | 2020-09-01 | 深圳氢时代新能源科技有限公司 | Composite proton exchange membrane, preparation method thereof and fuel cell |
| JPWO2020196720A1 (en) * | 2019-03-28 | 2020-10-01 | ||
| CN112408484A (en) * | 2020-11-23 | 2021-02-26 | 杭州富通电线电缆有限公司 | Tungsten trioxide hollow ball, preparation method thereof and application thereof in cable sheath |
| CN114985759A (en) * | 2022-05-24 | 2022-09-02 | 宁波江丰电子材料股份有限公司 | Method for preparing tungsten powder by using tungsten residual target |
| CN115784311A (en) * | 2022-11-24 | 2023-03-14 | 赣州市光华有色金属有限公司 | Method for recycling tungsten oxide through tungsten oxide waste |
| CN116573673A (en) * | 2023-06-08 | 2023-08-11 | 翁百成 | Preparation method of nano tungsten trioxide |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1286732C (en) * | 2004-11-11 | 2006-11-29 | 北京科技大学 | Preparation for nanometer anhydrous wolframic acid powder |
-
2007
- 2007-09-05 CN CN2007100499429A patent/CN101381106B/en not_active Expired - Fee Related
Cited By (35)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102190299A (en) * | 2010-03-18 | 2011-09-21 | 中国科学院上海硅酸盐研究所 | Preparation method of tungsten carbide nanopowder |
| CN102211789A (en) * | 2010-04-08 | 2011-10-12 | 中国科学院合肥物质科学研究院 | Method for preparing tungsten trioxide nano material |
| CN102211789B (en) * | 2010-04-08 | 2013-02-27 | 中国科学院合肥物质科学研究院 | Method for preparing tungsten trioxide nano material |
| CN102050493A (en) * | 2011-01-14 | 2011-05-11 | 中国科学院上海技术物理研究所 | Method for preparing WO3 nanocrystalline |
| CN102603007B (en) * | 2012-03-15 | 2014-06-18 | 合肥学院 | Preparation method of tungsten oxide nano powder and metal tungsten nano powder |
| CN102603007A (en) * | 2012-03-15 | 2012-07-25 | 合肥学院 | Preparation method of tungsten oxide nano powder and metal tungsten nano powder |
| CN102963932A (en) * | 2012-11-13 | 2013-03-13 | 江西稀有金属钨业控股集团有限公司 | Method for preparing ultrafine molybdenum trioxide |
| CN102963932B (en) * | 2012-11-13 | 2014-06-18 | 江西稀有金属钨业控股集团有限公司 | Method for preparing ultrafine molybdenum trioxide |
| CN103265081A (en) * | 2013-05-27 | 2013-08-28 | 合肥工业大学 | Method for preparing tungsten oxide nano single crystal by sol-gel method |
| CN103273544A (en) * | 2013-05-27 | 2013-09-04 | 安吉汉洲竹制品有限公司 | Nanometer tungsten oxide photocatalyst paper-base bamboo curtain manufacturing method and product thereof |
| CN103273544B (en) * | 2013-05-27 | 2015-04-15 | 安吉汉洲竹制品有限公司 | Nanometer tungsten oxide photocatalyst paper-base bamboo curtain manufacturing method and product thereof |
| CN103265081B (en) * | 2013-05-27 | 2015-02-04 | 合肥工业大学 | Method for preparing tungsten oxide nano single crystal by sol-gel method |
| CN103302310A (en) * | 2013-06-24 | 2013-09-18 | 刘亚静 | Tungsten nanopowder |
| CN103303978A (en) * | 2013-06-24 | 2013-09-18 | 刘亚静 | Preparation method of tungsten oxide (WO3) nanometer powder |
| CN103303979A (en) * | 2013-06-24 | 2013-09-18 | 刘亚静 | Tungsten oxide (WO3) nanopowder prepared by pyrolysing method |
| CN103302300A (en) * | 2013-06-24 | 2013-09-18 | 刘亚静 | Preparation method of tungsten nano powder |
| CN103302300B (en) * | 2013-06-24 | 2015-08-19 | 朱兰英 | A kind of preparation method of tungsten nanometer powder |
| CN103302310B (en) * | 2013-06-24 | 2015-11-25 | 朱兰英 | A kind of tungsten nanometer powder |
| CN103624269B (en) * | 2013-11-29 | 2015-08-26 | 北京航空航天大学 | A kind of nano-tungsten powder and employing collosol and gel hydrogen reduction method thereof prepare the method for nano-tungsten powder |
| CN103624269A (en) * | 2013-11-29 | 2014-03-12 | 北京航空航天大学 | Nanometer tungsten powder and method for preparing nanometer tungsten powder by adoption of sol-gel hydrogen reduction method |
| CN107381644B (en) * | 2017-08-22 | 2019-05-10 | 西安理工大学 | A kind of preparation method of one-dimensional tungsten trioxide nanowires |
| CN107381644A (en) * | 2017-08-22 | 2017-11-24 | 西安理工大学 | A kind of preparation method of one-dimensional tungsten trioxide nanowires |
| CN109987634A (en) * | 2017-12-30 | 2019-07-09 | 卢斌 | A kind of WO3The preparation method of aeroge |
| CN109100343A (en) * | 2018-07-02 | 2018-12-28 | 中国科学院合肥物质科学研究院 | The preparation method of tungsten oxide film |
| JPWO2020196720A1 (en) * | 2019-03-28 | 2020-10-01 | ||
| WO2020196720A1 (en) * | 2019-03-28 | 2020-10-01 | 株式会社 東芝 | Tungsten oxide powder and production method for tungsten oxide powder |
| CN113474293A (en) * | 2019-03-28 | 2021-10-01 | 株式会社东芝 | Tungsten oxide powder and method for producing tungsten oxide powder |
| JP7273949B2 (en) | 2019-03-28 | 2023-05-15 | 株式会社東芝 | Tungsten oxide powder and method for producing tungsten oxide powder |
| CN113474293B (en) * | 2019-03-28 | 2023-10-31 | 株式会社东芝 | Tungsten oxide powder and method for producing tungsten oxide powder |
| CN111613820A (en) * | 2020-05-08 | 2020-09-01 | 深圳氢时代新能源科技有限公司 | Composite proton exchange membrane, preparation method thereof and fuel cell |
| CN112408484A (en) * | 2020-11-23 | 2021-02-26 | 杭州富通电线电缆有限公司 | Tungsten trioxide hollow ball, preparation method thereof and application thereof in cable sheath |
| CN114985759A (en) * | 2022-05-24 | 2022-09-02 | 宁波江丰电子材料股份有限公司 | Method for preparing tungsten powder by using tungsten residual target |
| CN114985759B (en) * | 2022-05-24 | 2024-03-05 | 宁波江丰电子材料股份有限公司 | Method for preparing tungsten powder by utilizing tungsten residual target |
| CN115784311A (en) * | 2022-11-24 | 2023-03-14 | 赣州市光华有色金属有限公司 | Method for recycling tungsten oxide through tungsten oxide waste |
| CN116573673A (en) * | 2023-06-08 | 2023-08-11 | 翁百成 | Preparation method of nano tungsten trioxide |
Also Published As
| Publication number | Publication date |
|---|---|
| CN101381106B (en) | 2011-05-11 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101381106B (en) | Method for preparing nano tungsten trioxide powder | |
| Wang et al. | One-step synthesis of titanium oxide nanoparticles by spray pyrolysis of organic precursors | |
| CN103539210B (en) | A kind of preparation method of cobalt molybdate crystallite | |
| CN104986742B (en) | One species bead chain shape graphitization azotized carbon nano material and preparation method thereof | |
| US5833892A (en) | Formation of TiO2 pigment by spray calcination | |
| CN110180529B (en) | Preparation method for synthesizing photocatalytic material by using MOF as precursor | |
| CN103949192B (en) | A kind of method that microwave-assisted aerosol prepares hollow ball | |
| CN103084196B (en) | Preparation method and application of tantalum-based hierarchical structure hollow nanometer photocatalytic material | |
| CN104190423B (en) | A kind of spherical shape α-Fe2O3Preparation method | |
| CN104475078B (en) | Preparation method of nano rare-earth metal oxide/ carbon nano pipe composite catalyst | |
| CN110201655B (en) | One-step method for preparing hollow TiO2Method and application of nano-microspheres | |
| CN105032397A (en) | Method for synthesizing bismuth vanadate photocatalyst through starch self-combustion | |
| CN108654675A (en) | A kind of g-C3N4/TiO2(B) preparation method of complex microsphere | |
| CN102531015A (en) | Method for preparing porous aluminum oxide superfine powder | |
| CN104353461A (en) | Preparation method of high-specific surface nanometer magnesium ferrite catalyst material capable of being used in solid propellant | |
| CN107827153B (en) | A kind of preparation method of nanometer of silver vanadate | |
| CN104310466A (en) | Hollow titanium dioxide microsphere based on gel sphere precursor and preparation method of hollow titanium dioxide microsphere | |
| CN104649319B (en) | A kind of TiO 2(B) preparation method of nanosponges | |
| CN100460062C (en) | Preparation method of oxygen-producing photocatalyst of composite oxides | |
| CN106215968A (en) | A kind of carbon cladding CuO composite of the nitrogen that adulterates and preparation method thereof | |
| CN106219606A (en) | A kind of spherical Ag of nano flower3vO4preparation method | |
| CN106179431B (en) | A kind of zinc titanium metal composite oxide and its preparation and application | |
| CN108640144A (en) | A kind of yttrium oxide twin-stage nanosphere and preparation method thereof | |
| Chen et al. | Research on the Preparation of Nano SiO2–Al2O3–TiO2 Particle | |
| CN106140159A (en) | One quickly prepares bar-shaped AgVO3the method of nano-photocatalyst |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C17 | Cessation of patent right | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20110511 Termination date: 20130905 |