CN101624173A - Low-temperature solvent hot preparation method of indium tin oxide monodisperse nano powder - Google Patents
Low-temperature solvent hot preparation method of indium tin oxide monodisperse nano powder Download PDFInfo
- Publication number
- CN101624173A CN101624173A CN200910041342A CN200910041342A CN101624173A CN 101624173 A CN101624173 A CN 101624173A CN 200910041342 A CN200910041342 A CN 200910041342A CN 200910041342 A CN200910041342 A CN 200910041342A CN 101624173 A CN101624173 A CN 101624173A
- Authority
- CN
- China
- Prior art keywords
- tin
- indium
- low
- nano powder
- indium oxide
- 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
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Abstract
The invention discloses a low-temperature solvent hot preparation method of indium tin oxide monodisperse nano powder, comprising the following steps: the glycol suspension of indium tin hydroxide is put into a reaction kettle for low-temperature solvent hot reaction; after reaction ends, the obtained precipitate is centrifugated for separation, cleaned and dried to obtain indium oxide or indium tin oxide monodisperse nano powder; the low-temperature solvent hot reaction is carried out at the temperature of 180-300 DEG C for 0.5-20h. The invention uses simple low-temperature solvent thermosynthesis method to finish the reaction in one step, which has simple procedure and easy operation; in addition, the invention has low reaction temperature, no calcination, simple device, low cost, safe operation and little pollution; the average grain diameter of the prepared indium tin and ITO powder is smaller than 100nm, grain diameter distribution range is narrow and dispersity is favourable.
Description
Technical field
The invention belongs to technical field of semiconductor, the low-temperature solvent heat preparation method of particularly a kind of tin indium oxide (ITO) dispersed nano powder.
Background technology
Be accompanied by the development of liquid crystal display, indium tin oxide (ITO) requirement that is used for transparency electrode sharply increases.At present, developed country in the world is as Japan, the U.S., France etc., and the indium with 90% is used to prepare the material of ITO.They generally adopt indium tin oxide to make target, with direct current magnetron sputtering process target are made ito thin film then.This film is to visible transparent, and energy strong reflection infrared light has low film resistance, thereby obtains increasingly extensive application at aspects such as liquid crystal display, heat-protecting glass, solar cell and gatherer, the frost prevention of vehicle window mist elimination.For preparation target used ito powder, require very strictly, not only want the purity height, and fine size, dispersive property are good.The next generation utilizes in the printing technique production process ito powder is got granularity and dispersedly has a higher requirement.The method of relevant tin indium oxide nano powder preparation has much in recent years, as hydro-thermal method, micro emulsion method, spray burning method and chemical precipitation method etc., liquid mist oxidizing fire method, liquid phase chemical coprecipitation and homogeneous coprecipitation method are only arranged but can be used in the method that industrial production prepares the ITO powder.Preparation method as the ITO nano-powder of open source literature report mainly contains:
1, " preparation method of the indium oxide powder of crystal with controllable crystal forms ", Chinese patent＜application number〉200710044189, set forth being prepared as follows based on the indium oxide powder of crystal with controllable crystal forms: (1) will contain indium ion and a certain amount of transition metal ions (Fe, Co, Ni, Cu, Cr, among the Mn one or more) alcoholic solution and alkali alcosol mix; (2) it is centrifugal to obtain suspension, the washing of precipitate that obtains, and drying at 300-500 ℃ of temperature lower calcination, can obtain the indium oxide nano powder of controlled crystal formation.Described alcoholic solution is preferentially recommended methyl alcohol or ethanol for low polarity alcohol.The mass percentage concentration of indium salt alcoholic solution is 0.5～10%, and the atom percentage concentration of containing transition metal ion is 0.1～20%.
2, " chemical coprecipitation prepares nano-ITO powder and structural characterization ", " functional material ", 2003,26 (4).Introduced with InCl in the document
34H
2O and SnCl
45H
2O is a raw material, adopts chemical coprecipitation to prepare nanoscale ITO powder.Utilize laboratory facilities such as TEM, XRD, IR, particles distribution instrument that pattern, thing phase, the granularity of powder are characterized, the influence of calcining heat to powder thing phase and granularity has been discussed.Result of study shows: when calcining heat＞300 ℃, can obtain crystal formation is cube In
2O
3The ball shaped nano ITO powder of structure, the about 30nm of particle diameter.
3, people such as Japanese Kochi University Yanagisawa is in document (Journal of Materials Research, 2000,15 (6): 1404-1408) mentioned a kind of method of Hydrothermal Preparation ITO powder.This method is taked ammonia precipitation process indium (tin) salting liquid, and the hydro-thermal presoma-indium hydroxide (tin) that generates is carried out hydro-thermal reaction (300 ℃), obtains the ITO nano-powder through filtration, vacuum drying, calcining at last.In this method preparation process because to introduce ammoniacal liquor be precipitating reagent, its hydrothermal temperature that obtains (being not less than 300 ℃), simultaneously for indium and tin are precipitated fully, need to use excess of ammonia water sedimentation agent, thereby cause meeting effusion ammonia in the high-temperature water thermal process, so that the voltage endurance capability of hydro-thermal reaction equipment needs to improve greatly (theoretical pressure just is not less than 20MPa), and the introducing of ammoniacal liquor has caused the decline of water heating apparatus high-temperature anticorrosion ability.
4, " In
2O
3The hydrothermal preparing process of ITO dispersed nano powder "; Chinese patent＜application number〉200310111223; set forth based on indium oxide; being prepared as follows of ITO dispersed nano powder: indium metal (tin) is dissolved in the inorganic acid; handle the colloidal solution that obtains with anion exchange resin after being made into certain density mixed solution; the colloidal solution that will isolate resin places autoclave, after 180～260 ℃ of hydrothermal temperatures react 4～24h down, product is washed with pure water, vacuum filtration, and through 100-105 ℃ of drying 6～12h, can make In behind 500～1000 ℃ of calcining 2～4h
2O
3, ITO dispersed nano powder.Result of study shows: diameter of particle≤100nm.
We can recognize from above-mentioned document or patent, the method of the existing various ITO of preparation powders all has common shortcoming: no matter be to use chemical coprecipitation, or hydro-thermal method, all need two-step reaction, at first make predecessor indium tin hydroxide precipitation, obtain the ITO powder 300-500 ℃ of calcining then at low temperature.The technological process complexity; Owing to need calcining, therefore required temperature is all very high; It is serious that high-temperature calcination also must cause product particle to reunite, and is unfavorable for next step application.
Summary of the invention
At the deficiency that above-mentioned prior art exists, primary and foremost purpose of the present invention is to provide the low-temperature solvent heat preparation method of a kind of tin indium oxide (ITO) dispersed nano powder.
Another object of the present invention is to provide a kind of tin indium oxide dispersed nano powder of method for preparing.
The objective of the invention is to be achieved through the following technical solutions: a kind of low-temperature solvent heat preparation method of tin indium oxide dispersed nano powder is characterized in that comprising following operating procedure: the glycolic suspension of indium tin hydroxide is put into reactor carry out the low-temperature solvent thermal response; It is centrifugal that reaction finishes the back, washing, and drying obtains indium oxide or tin indium oxide dispersed nano powder; Described low-temperature solvent thermal response is to react 0.5～20h under 180～300 ℃ of temperature conditions; It is 0～20% tin oxide (when the mass percent concentration of tin oxide was 0, product was indium oxide) that described tin indium oxide dispersed nano powder contains mass percent concentration.
The glycolic suspension of described indium tin hydroxide is that the concentration of indium tin oxide presoma (indium tin hydroxide) with mass volume ratio≤0.1g/ml is dispersed in the ethylene glycol; Described indium tin oxide presoma is to adopt chemical precipitation method, hydro-thermal method, prepared with microemulsion reactor to obtain indium metal+metallic tin or solubility indium salt+solubility pink salt.
The glycolic suspension of described indium tin hydroxide is to prepare according to the following steps:
(1) indium metal+metallic tin or solubility indium salt+solubility pink salt are dissolved in the inorganic acid, obtaining indium and tin metal ion concentration is the mixed solution of 0.14～1.4mol/L;
(2) step (1) gained mixed solution is added in the ethylene glycol, mix;
(3) regulate pH value to 6.0～11.0, obtain the glycolic suspension of indium tin hydroxide.
The described inorganic acid of step (1) is one or more in hydrochloric acid, nitric acid and the sulfuric acid.
Described inorganic acid is that the volume ratio of described mixed solution of step (2) and ethylene glycol is 0.1: 10～2: 10.
The described adjusting of step (3) pH value is to regulate with NaOH, potassium hydroxide, urea or ammoniacal liquor.
Described drying is oven dry or vacuum drying, and dry temperature is 40～200 ℃, and the dry time is 1～48h.
The particle diameter of the indium oxide of method for preparing or tin indium oxide dispersed nano powder is 10～200nm.
Above-mentioned indium oxide or tin indium oxide dispersed nano powder are applied to prepare the anti-creme of liquid crystal display material, heat-protecting glass, solar cell, solar collector or vehicle window mist elimination.
The present invention compared with prior art has following advantage and beneficial effect: (1) utilizes simple low temperature solvent thermal synthesis method, and single step reaction can be prepared indium oxide, ITO nanometer powder, and operation is simple, easy operating; (2) the required temperature of course of reaction is low, can be low to moderate 180 ℃, and need can not obtain product through calcining, advantage such as have that equipment is simple, cost is low, handling safety, pollution are little; (3) Zhi Bei indium oxide, ITO powder average grain diameter can be less than 100nm,, particle size distribution range is narrow, and is dispersed fine; (4) preparation technology's flow process is simple, is suitable for large-scale industrial production.
The specific embodiment
The present invention is described in further detail below in conjunction with embodiment, but embodiments of the present invention are not limited thereto.
Embodiment 1
(1) 38g InCl
34H
2O and 4.65g SnCl
45H
2O uses earlier the 100mL dissolving with hydrochloric acid, gets mixed solution;
(2) step (1) gained mixed solution is added 4L ethylene glycol and make solvent, mix;
(3) under stirring, slowly add mass percent concentration and be 25% NH
3H
2O is adjusted to 7.0 with the pH value, stirs, and obtains the glycolic suspension of indium tin hydroxide;
(4) glycolic suspension with step (3) gained indium tin hydroxide moves on in the reactor, under 200 ℃ of conditions, and reaction 2h; After reaction finishes, the gained sediment is carried out centrifugal, washing, 60 ℃ of vacuum drying 24h promptly get tin indium oxide dispersed nano powder product, wherein contain mass percent concentration and be 10% tin oxide.The nano-ITO powder that makes is observed average grain diameter＜100nm under ESEM, the particle size range that adopts the nano particle size analyzer to record is 10-200nm.
Embodiment 2
(1) 49.5g In (NO
3)
34H
2O and 6.0g Sn (NO
3)
45H
2O uses earlier the 100mL nitric acid dissolve, gets mixed solution;
(2) step (1) gained mixed solution is added 10L ethylene glycol and make solvent, mix;
(3) under stirring, slowly splash into NaOH the pH value is adjusted to 7.0, stir, obtain the glycolic suspension of indium tin hydroxide;
(4) glycolic suspension with step (3) gained indium tin hydroxide moves on in the reactor, under 200 ℃ of conditions, and reaction 4h; After reaction finishes, the gained sediment is carried out centrifugal, washing, 40 ℃ of vacuum drying 48h promptly get tin indium oxide dispersed nano powder product, wherein contain mass percent concentration and be 10% tin oxide.
Embodiment 3
(1) 23.16g indium metal and 5.51g metallic tin are used earlier the 100mL sulfuric acid dissolution, get mixed solution;
(2) step (1) gained mixed solution is added 2L ethylene glycol and make solvent, mix;
(3) under stirring, with potassium hydroxide the pH value is adjusted to 11.0, stir, obtain the glycolic suspension of indium tin hydroxide;
(4) glycolic suspension with step (3) gained indium tin hydroxide moves on in the reactor, under 180 ℃ of conditions, and reaction 20h; After reaction finishes, the gained sediment is carried out centrifugal, washing, 100 ℃ of vacuum drying 48h promptly get tin indium oxide dispersed nano powder product, wherein contain mass percent concentration and be 20% tin oxide.
Embodiment 4
(1) the 25.3g indium metal is used earlier the 100mL nitric acid dissolve, get mixed solution;
(2) step (1) gained mixed solution is added 8L ethylene glycol and make solvent, mix;
(3) under stirring, with solid urea the pH value is adjusted to 6.0, stir, obtain the glycolic suspension of indium tin hydroxide;
(4) glycolic suspension with step (3) gained indium tin hydroxide moves on in the reactor, under 240 ℃ of conditions, and reaction 5h; After reaction finishes, the gained sediment is carried out centrifugal, washing, 60 ℃ of vacuum drying 48h promptly get the indium oxide product.
Embodiment 5
(1) 41g InCl
34H
2O and 1.4g SnCl
45H
2O adopts the presoma that chemical precipitation method prepares indium tin oxide;
(2) be that the concentration of 0.1g/ml is dispersed in the ethylene glycol with step (1) gained indium tin oxide presoma, obtain the glycolic suspension of indium tin hydroxide with the mass volume ratio;
(3) glycolic suspension with step (2) gained indium tin hydroxide moves on in the reactor, under 240 ℃ of conditions, and reaction 5h; After reaction finishes, the gained sediment is carried out centrifugal, washing, 100 ℃ of vacuum drying 20h promptly get tin indium oxide dispersed nano powder product, wherein contain mass percent concentration and be 3% tin oxide.
Embodiment 6
(1) 40g InCl
34H
2O and 2.3g SnCl
45H
2O adopts Hydrothermal Preparation indium tin oxide presoma;
(2) be that the concentration of 0.08g/ml is dispersed in the ethylene glycol with step (1) gained indium tin oxide presoma, obtain the glycolic suspension of indium tin hydroxide with the mass volume ratio;
(3) glycolic suspension with step (2) gained indium tin hydroxide moves on in the reactor, under 300 ℃ of conditions, and reaction 0.5h; After reaction finishes, the gained sediment is carried out centrifugal, washing, 110 ℃ of vacuum drying 24h promptly get tin indium oxide dispersed nano powder product, wherein contain mass percent concentration and be 5% tin oxide.
Embodiment 7
(1) 38.9g InCl
34H
2O and 3.7g SnCl
45H
2O adopts prepared with microemulsion reactor indium tin oxide presoma;
(2) be that the concentration of 0.02g/ml is dispersed in the ethylene glycol with step (1) gained indium tin oxide presoma, obtain the glycolic suspension of indium tin hydroxide with the mass volume ratio;
(3) glycolic suspension with step (2) gained indium tin hydroxide moves on in the reactor, under 240 ℃ of conditions, and reaction 5h; After reaction finishes, the gained sediment is carried out centrifugal, washing, 200 ℃ of vacuum drying 4h promptly get tin indium oxide dispersed nano powder product, wherein contain mass percent concentration and be 8% tin oxide.
The foregoing description is a preferred implementation of the present invention; but embodiments of the present invention are not restricted to the described embodiments; other any do not deviate from change, the modification done under spiritual essence of the present invention and the principle, substitutes, combination, simplify; all should be the substitute mode of equivalence, be included within protection scope of the present invention.
Claims (9)
1, a kind of low-temperature solvent heat preparation method of tin indium oxide dispersed nano powder is characterized in that comprising following operating procedure: the glycolic suspension of indium tin hydroxide is put into reactor carry out the low-temperature solvent thermal response; It is centrifugal that reaction finishes the back, washing, and drying obtains tin indium oxide dispersed nano powder; Described low-temperature solvent thermal response is to react 0.5～20h under 180～300 ℃ of temperature conditions; It is 0～20% tin oxide that described tin indium oxide dispersed nano powder contains mass percent concentration.
2, according to the low-temperature solvent heat preparation method of the described a kind of tin indium oxide dispersed nano powder of claim 1, it is characterized in that: the glycolic suspension of described indium tin hydroxide is that the concentration of indium tin oxide presoma with mass volume ratio≤0.1g/ml is dispersed in the ethylene glycol; Described indium tin oxide presoma is to adopt chemical precipitation method, hydro-thermal method or prepared with microemulsion reactor to obtain indium metal+metallic tin or solubility indium salt+solubility pink salt.
3, according to the low-temperature solvent heat preparation method of the described a kind of tin indium oxide dispersed nano powder of claim 1, it is characterized in that: the glycolic suspension of described indium tin hydroxide is to prepare according to the following steps:
(1) indium metal+metallic tin or solubility indium salt+solubility pink salt are dissolved in the inorganic acid, obtaining indium and tin metal ion concentration is the mixed solution of 0.14～1.4mol/L;
(2) step (1) gained mixed solution is added in the ethylene glycol, mix;
(3) regulate pH value to 6.0～11.0, obtain the glycolic suspension of indium tin hydroxide.
4, according to the low-temperature solvent heat preparation method of the described a kind of tin indium oxide dispersed nano powder of claim 3, it is characterized in that: the described inorganic acid of step (1) is one or more in hydrochloric acid, nitric acid and the sulfuric acid.
5, according to the low-temperature solvent heat preparation method of the described a kind of tin indium oxide dispersed nano powder of claim 3, it is characterized in that: the volume ratio of described mixed solution of step (2) and ethylene glycol is 0.1: 10～2: 10.
6, according to the low-temperature solvent heat preparation method of the described a kind of tin indium oxide dispersed nano powder of claim 3, it is characterized in that: the described adjusting of step (3) pH value is to regulate with NaOH, potassium hydroxide, urea or ammoniacal liquor.
7, according to the low-temperature solvent heat preparation method of the described a kind of tin indium oxide dispersed nano powder of claim 1, it is characterized in that: described drying is oven dry or vacuum drying, and dry temperature is 40～200 ℃, and the dry time is 1～48h.
8, a kind of tin indium oxide dispersed nano powder according to each described method preparation of claim 1～7, it is characterized in that: the particle diameter of described indium oxide or tin indium oxide dispersed nano powder is 10～200nm.
9, tin indium oxide dispersed nano powder according to claim 8 is applied to prepare the anti-creme of liquid crystal display material, heat-protecting glass, solar cell, solar collector or vehicle window mist elimination.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2009100413427A CN101624173B (en) | 2009-07-23 | 2009-07-23 | Low-temperature solvent hot preparation method of indium tin oxide monodisperse nano powder |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2009100413427A CN101624173B (en) | 2009-07-23 | 2009-07-23 | Low-temperature solvent hot preparation method of indium tin oxide monodisperse nano powder |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101624173A true CN101624173A (en) | 2010-01-13 |
| CN101624173B CN101624173B (en) | 2011-11-16 |
Family
ID=41520190
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2009100413427A Expired - Fee Related CN101624173B (en) | 2009-07-23 | 2009-07-23 | Low-temperature solvent hot preparation method of indium tin oxide monodisperse nano powder |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101624173B (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102786080A (en) * | 2012-07-18 | 2012-11-21 | 中国科学院福建物质结构研究所 | Indium tin oxide compound, its preparation method and its photocatalytic application |
| CN102899040A (en) * | 2011-07-26 | 2013-01-30 | 北京化工大学 | Low temperature preparation method of monodisperse doped tin oxide nanoparticles |
| CN103787404A (en) * | 2013-12-31 | 2014-05-14 | 浙江大学 | Preparation method, production and application of mono-dispersed indium tin oxide nano crystal with controllable size |
| CN104692452A (en) * | 2013-12-10 | 2015-06-10 | 中国科学院苏州纳米技术与纳米仿生研究所 | Method for preparing tin indium oxide nano-crystal |
| CN108002427A (en) * | 2017-11-29 | 2018-05-08 | 广西生富锑业科技股份有限公司 | A kind of preparation method of tin indium oxide nano-powder |
| CN113277549A (en) * | 2021-06-15 | 2021-08-20 | 先导薄膜材料有限公司 | Indium tin oxide powder and preparation method thereof |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100525307B1 (en) * | 2002-03-29 | 2005-11-02 | (주)나울 | Thermal protection glassing using nanopartics |
| CN1622283A (en) * | 2004-12-15 | 2005-06-01 | 贺平 | Method for preparing composite oxide semiconductor nano material |
| CN100465099C (en) * | 2005-12-08 | 2009-03-04 | 华东理工大学 | Method for preparing ITO powder with high sintering activity |
| CN101041459A (en) * | 2007-03-12 | 2007-09-26 | 宁夏大学 | Low-temperature preparation method of indium oxide tin super fined powder |
-
2009
- 2009-07-23 CN CN2009100413427A patent/CN101624173B/en not_active Expired - Fee Related
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102899040A (en) * | 2011-07-26 | 2013-01-30 | 北京化工大学 | Low temperature preparation method of monodisperse doped tin oxide nanoparticles |
| CN102899040B (en) * | 2011-07-26 | 2014-06-18 | 北京化工大学 | Low temperature preparation method of monodisperse doped tin oxide nanoparticles |
| CN102786080A (en) * | 2012-07-18 | 2012-11-21 | 中国科学院福建物质结构研究所 | Indium tin oxide compound, its preparation method and its photocatalytic application |
| CN104692452A (en) * | 2013-12-10 | 2015-06-10 | 中国科学院苏州纳米技术与纳米仿生研究所 | Method for preparing tin indium oxide nano-crystal |
| CN104692452B (en) * | 2013-12-10 | 2016-04-27 | 中国科学院苏州纳米技术与纳米仿生研究所 | The preparation method that a kind of tin indium oxide is nanocrystalline |
| CN103787404A (en) * | 2013-12-31 | 2014-05-14 | 浙江大学 | Preparation method, production and application of mono-dispersed indium tin oxide nano crystal with controllable size |
| CN103787404B (en) * | 2013-12-31 | 2015-05-20 | 浙江大学 | Preparation method, production and application of mono-dispersed indium tin oxide nano crystal with controllable size |
| CN108002427A (en) * | 2017-11-29 | 2018-05-08 | 广西生富锑业科技股份有限公司 | A kind of preparation method of tin indium oxide nano-powder |
| CN108002427B (en) * | 2017-11-29 | 2019-05-24 | 广西生富锑业科技股份有限公司 | A kind of preparation method of tin indium oxide nano-powder |
| CN113277549A (en) * | 2021-06-15 | 2021-08-20 | 先导薄膜材料有限公司 | Indium tin oxide powder and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN101624173B (en) | 2011-11-16 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101624173B (en) | Low-temperature solvent hot preparation method of indium tin oxide monodisperse nano powder | |
| CN104148047B (en) | Macro preparation method for carbon doped zinc oxide-based visible-light catalyst | |
| CN101234750B (en) | Method of preparing superfine micro-particle and nano granule | |
| CN102408120B (en) | Method for preparing high-purity ultrafine lithium-carbonate micro powder | |
| CN106335922B (en) | A kind of preparation method of the ultra-thin anatase nanometer sheet self-assembly microspheres in height (001) face | |
| CN109248695B (en) | Oxygen vacancy mediated Bi-based layered nitrogen fixation photocatalyst and preparation method thereof | |
| CN100593019C (en) | Tin dioxide powder body doped with antimony and preparing method thereof | |
| CN101117236B (en) | Method for preparing crystal system controlled indium oxide powder | |
| CN100552094C (en) | The preparation method of the indium oxide nanocrystalline that pattern is controlled | |
| CN1237006C (en) | In2O3 and ITO monodisperse nano powder hydrothermal preparation method | |
| CN101049966A (en) | Method for producing powder in micron order of bismuth oxide | |
| CN108059187B (en) | Low hexavalent chromium separated copper-chromium black pigment and preparation method and application thereof | |
| CN109133144A (en) | A kind of preparation method of monodisperse ultra-small grain size ceria nano-crystalline | |
| CN101570349A (en) | Super capacitor material NiO synthesis method | |
| CN101817086A (en) | Novel process for converting silver-containing scarp to nano-silver | |
| CN103613958B (en) | Environment-friendly titanium pigment prepared by using complexation-precipitation process | |
| CN111099654A (en) | Nano ZnSnO3Preparation method of gas-sensitive material | |
| CN103193254B (en) | Novel technology for simultaneously preparing rodlike and sheetlike nano-sized magnesium hydroxide | |
| Mao et al. | Nano-CaCO3 synthesis by tangential jet from carbide slag | |
| CN102491418B (en) | Preparation method of dumbbell-shaped bismuth vanadate | |
| CN114560490A (en) | Preparation method of high-purity spheroidal nano lanthanum oxide powder | |
| CN103623770B (en) | Core-shell type amorphous metal oxide adsorbent, as well as preparation method and application thereof | |
| CN107755712B (en) | Method for preparing metal antimony powder | |
| CN100343173C (en) | Prepn of monodisperse nanometer In-Sn oxide powder | |
| CN109225196A (en) | The precipitation method prepare the method and its application of Zinc modified bismuth oxide composite photo-catalyst |
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 | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20111116 Termination date: 20140723 |
|
| EXPY | Termination of patent right or utility model |