CN1171796C - Oxidation and coprecipitation process of preparing Sb-doped nano tin dioxide - Google Patents
Oxidation and coprecipitation process of preparing Sb-doped nano tin dioxide Download PDFInfo
- Publication number
- CN1171796C CN1171796C CNB021354421A CN02135442A CN1171796C CN 1171796 C CN1171796 C CN 1171796C CN B021354421 A CNB021354421 A CN B021354421A CN 02135442 A CN02135442 A CN 02135442A CN 1171796 C CN1171796 C CN 1171796C
- Authority
- CN
- China
- Prior art keywords
- washing
- presoma
- reaction
- doped
- oxidation
- 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.)
- Expired - Fee Related
Links
Images
Abstract
The present invention relates to a method of preparing Sb2O5-doped nanometer SnO2. In the method, a Sb-doped nanometer SnO2 is prepared from SnCl4, SbCl3, H2O2 and ammonia water by an oxidation coprecipitation method under a suitable reaction condition; antimony-doped nanometer SnO2 with different particle size is obtained by heat treatment of the precursor Sn(OH)4, Sb(OH)5 at a different temperature; an organic substance can be dissolved in water, and can be decomposed and volatilized during the continued calcination process; a precursor colloidal solution to be separated can be separated in a short time by adding a certain amount of the organic substance(ethanol) when the precursor solution is washed and separated. The method creates a condition for the continuous production and bulk production of Sb2O5-doped nanometer SnO2; the washing separation method provides a novel process principle and a path for the washing separation of a hydroxide ultrafine (nanometer) body which is inorganic and insoluble in water; the method also provides a reference for washing and separating precipitates when the nanometer powder is prepared by other precipitation methods at present.
Description
Technical field
The invention belongs to the nano-stannic oxide preparing technical field, specifically is a kind of method for preparing Sb-doped nano tin dioxide with oxidation and coprecipitation.
Prior art
SnO
2Be present modal gas sensory material, it all has quite high sensitivity to many inflammable gass as hydrogen, carbon monoxide, methane, ethanol or aromatic hydrocarbon, and this utilizes semiconductor surface to adsorb to control the gas sensing mechanism of specific conductivity relevant with it.Adulterated SnO
2Superfine powder has bigger specific surface area, and by the gas sensor that this powder is made, sensitivity and selectivity can improve greatly.
Prepare SnO at present
2Method the precipitator method and sol-gel method etc. are arranged, when preparing superfine powder, the precipitator method have technology simple, characteristics such as cost is low, but be difficult to washing and isolating drawback (Chinese Journal of Inorganic Chemistry, 2000:16 (2): 213-217) using the precipitator method to prepare to exist precipitation in the nano-powder process.Oxidation and coprecipitation prepares Sb-doped nano SnO
2Also make an exception in the powder process to exist to precipitate and be difficult to washing and isolating drawback.Exist some contradictions between control of precipitation granularity and filtration washing performance, obtain ultra-fine grain, then strainability is relatively poor, otherwise then granularity is difficult to obtain assurance.This in fact also is the common drawbacks of all washing separating ultra-fine body processes; When adopting the method head it off of centrifugation or suction filtration (decompression), waste time and energy, and can only obtain few products at every turn, can not satisfy that industrialization is continuous, batch production requirement.
Summary of the invention
The present invention has overcome the preparation of oxidation and coprecipitation method and has mixed Sb
2O
5SnO
2Exist precipitation in the nano powder and be difficult to washing and isolating drawback, for inorganic, indissoluble oxyhydroxide ultra-fine (nanometer) body washing separation provide a kind of separation method; Provide the preparation of oxidation and coprecipitation method to mix Sb
2O
5SnO
2The suitable condition of nano-powder.
The present invention adopts following scheme to realize that oxidation and coprecipitation prepares the method for Sb-doped nano tin dioxide, may further comprise the steps: under (1) mechanical stirring, with SnCl
4And SbCl
3Mixing solutions, H
2O
2Solution and ammonia soln, under temperature of reaction, splash in the solution that contains anti-agglomeration agent-polyoxyethylene glycol, control entire reaction course PH, after reaction is finished, obtain containing the colloidal solution of presoma, (2) the presoma colloidal solution of gained obtains dry purified presoma Sn (OH) after centrifugation, washing, dehydration, vacuum-drying
4, Sb (OH)
5, (3) dry purified presoma Sn (OH)
4, Sb (OH)
5Behind the porphyrize, under differing temps, calcine, promptly get different big or small Nanometer-sized Antimony-doped tindioxide powders at last, it is characterized in that: separate presoma Sn (OH) in washing
4, Sb (OH)
5Process in, at first use deionization washing, when washing the suction filtration velocity of separation when being lower than 9ml/min, the volumn concentration that contains that re-uses with the deionized water preparation is that the washings of 6-20% ethanol or acetone or polyoxyethylene glycol is washed no Cl
-Till, obtain nano antimony doped SnO
2Powder needs to obtain even particle distribution and tiny presoma Sn (OH)
4, Sb (OH)
5, and this moment the strainability variation.Find in the experiment that filtration velocity is not only relevant with the thickness of particle, also depend on filter cake thickness, temperature, liquid-solid ratio etc.By decompress filter, use quantitatively quick filter paper more many soon than common qualitative filter paper suction filtration speed.However, along with the increase of washing times, suction filtration speed is more and more slower, so that can't separate.This is that surface energy is big, easily forms continuous gluing by hydrogen bond and water between particle, causes precipitating thickness, and is not easily separated because along with the increasing of washing times, the anti-agglomeration agent-polyoxyethylene glycol of precipitation surface absorption is almost all washed off, and colloidal particle is tiny.If this moment is according to the character of presoma, it is water-soluble to add a spot of energy in the distilled water of washing separation presoma, nontoxic, and evaporable organic substance such as ethanol, acetone can be decomposed in follow-up calcination process, even the polyoxyethylene glycol that just has been washed etc., stir about 10min on the magnetic stirrer, tiny colloid ion is because surface energy is big, can adsorb materials such as ethanol again by hydrogen bond, reduced surface energy, gluing is inhibited, formation be precipitated as independently small agglomerates, so sedimentation is fast, filtration washing is easy.Experimental results show that, with ethanol or acetone or polyethyleneglycol content increase, suction filtration speed is fast more, but we mainly are to use the impurity on the deionized water wash presoma, the content of ethanol or acetone or polyoxyethylene glycol is not The more the better like this, experimental results show that ethanol or acetone or polyoxyethylene glycol volume percent reach 20% at the most and be advisable.After the impurity washes clean, again with the dehydrated alcohol dehydration, vacuum-drying, calcining promptly gets product.
Oxidation and coprecipitation prepares Sb-doped nano SnO
2Suitable reaction conditions: keep SnCl
4And SbCl
3Mixing solutions in SnCl
4Concentration be 2moll
-1, temperature of reaction is a room temperature to 50 ℃, and the molecular weight of polyoxyethylene glycol is 6000, and the solution that contains anti-agglomeration agent-polyoxyethylene glycol (PEG) is 50ml, and the control of PH adopts and splash into the excess of ammonia aqueous solution, form buffered soln controls; Calcining temperature is not less than 420 ℃.Temperature of reaction is controlled at room temperature to 50 ℃, can obtain than the more purified presoma Sn of room temperature (OH)
4, Sb (OH)
5
Because H
2O
2When the temperature that is higher than 53 ℃, take place to decompose strongly, so the selection of temperature can not be higher than 53 ℃ in this experiment, can adopt room temperature to 50 ℃, there is certain temperature can obtain than the more purified presoma Sn of room temperature (OH)
4, Sb (OH)
5
The molecular weight size of polyoxyethylene glycol elects 6000 or 4000 as, and because of the increase of PEG molecular weight, the particle diameter of nano-powder is more little, is 6000 so preferably select PEG for use.
The control major requirement of solution PH: precipitated thing can precipitate fully under the PH condition of being controlled; The speed that splashes into during reaction is unsuitable too fast, excessive velocities, precipitation is grown up rapidly, then be adsorbed on earlier precipitation surface foreign ion have little time to leave precipitation, so just be absorbed in the precipitation crystals, the precipitation that this phenomenon causes is impure can't flush away;
Should adopt progressively the method that heats up during calcining, can make like this that incendive organism fully burns in the presoma.Because 420 ℃ of corresponding Sb-doped nano SnO
2Crystallization temperature, so calcining temperature can not be lower than 420 ℃.
Ethanol used in the present invention, acetone, the volumn concentration of polyoxyethylene glycol etc. are 6-20%.
The present invention has the following advantages and effect, and 1, provide a kind of separation method for the washing of inorganic, indissoluble oxyhydroxide ultra-fine (nanometer) body separates, also the precipitation that nano-powder exists is difficult to washing, separation is offered reference for other precipitator method prepare simultaneously.2, washing presoma Sn (OH)
4, Sb (OH)
5In time, adds reagent such as ethanol and the washing of presoma separated finish fast, and this method be continuously, batch process Sb
2O
5Adulterated nano SnO
2Create condition, had simple, the less investment of equipment, helped the characteristics of suitability for industrialized production; 3, to prepare the used prices such as ethanol of Sb-doped nano tin dioxide washing presoma cheap, nontoxic and easy to be recycled for oxidation and coprecipitation.
The present invention washs Sn (OH)
4, Sb (OH)
5The principle method be equally applicable to that other is inorganic, the washing of the ultra-fine oxyhydroxide of indissoluble separates.
When adopting indoor temperature solid phase method to prepare high-purity, ultrafine aluminium hydroxide, with aluminum nitrate and tween-80, (aluminum nitrate and sodium hydroxide mol ratio are 1: 3 to sodium hydroxide,) be placed on respectively in the agate mortar fully levigate after, rapidly aluminum nitrate is mixed with sodium hydroxide with the mixture of tween-80, fully ground 20 minutes, reactant is thinning by solid, after become thick, priority is with distilled water and contain a small amount of absolute ethanol washing, dewater with absolute ethanol washing at last, product is placed in 110 ℃ of baking ovens dry, high-purity, ultra fine aluminium hydroxide is last
Preparation high pure and ultra-fine aluminium hydroxide, reaction equation is:
, after reaction is finished, obtain containing a small amount of reactant and NaNO
3Product, product A l (OH)
3Need just can obtain high-purity, ultra-fine Al (OH) through thorough washing
3Experimental results show that: product is through filtration under diminished pressure, uses fast quantification filter paper, and speed is very slow during with deionized water wash to the four times, at this moment, is containing Al (OH)
3Colloidal solution in to add volume percent be 10% ethanol, stirred about 10 minutes on the magnetic stirrer, allow Al (OH)
3Fully ethanol is gone up in absorption, decompress filter, and 100ml liquid to be separated all separated in five minutes.After five washings, obtaining purity is 98.98%, and mean particle size is the high pure and ultra-fine Al (OH) of 300nm
3
Description of drawings
Fig. 1 calcines through differing temps for presoma, the Sb-doped nano SnO of gained
2X-ray diffractogram.
Fig. 2 is the Sb-doped nano SnO of presoma through two hours gained of 600 ℃ of thermal treatments
2The transmission electron microscope picture of powder.
Embodiment
Embodiment 1
Experimental technique process: under mechanical stirring, with 2molL
-1SnCl
4(analytical pure) and 6% (mass percent) SbCl
3Mixing solutions 25ml, the 10%H of (analytical pure)
2O
2Solution 10ml and by 1: 2 the dilution after strong aqua 50ml, splashing into 50ml under 45 ℃ simultaneously contains in the solution of 6% polyoxyethylene glycol, control entire reaction course PH remains on after 9.0～9.1. medicine drips off, continue reaction 30min, the throw out of gained is washed till no Cl with deionized water and the deionization that contains small amount of ethanol
-After, wash 3 times with dehydrated alcohol again, in the dry 3h of 85 ℃ of vacuum (690mmHg), under differing temps, calcine 2h behind the porphyrize, what promptly get the different grain size size mixes antimony SnO
2Nanopowder.The chemical reaction that is taken place in the experiment is:
Presoma is calcined under differing temps, and gained is mixed antimony SnO
2The nanopowder X-ray diffractogram is seen accompanying drawing 1, according to the Scherrer formula:
D
hkl＝Kλ/βcosθ，
In the formula: K gets 0.89, and λ=0.15418nm, β are the halfwidth that the halfwidth of sample diffracted ray is deducted corresponding 2 θ place standard model diffraction peaks.(110) crystal face is adopted slow sweep, is standard with the diffraction peak of Si standard specimen, calculates under the different calcining temperatures perpendicular to the mean grain size D110 of (110) crystal face, the results are shown in Table 1
Table 1 D
110And the relation between the calcining temperature
| T(℃) | 200 | 430 | 600 | 650 |
| D 110(nm) | Amorphous | 4.4 | 6.1 | 8.2 |
From accompanying drawing 1 and table 1 as seen: along with the rising of calcining temperature, diffracted intensity and mean grain size increase.
Accompanying drawing 2 is that presoma is through two hours gained Sb-doped nanos of 600 ℃ of thermal treatment SnO
2Transmission electron microscope picture.Sample shape is roughly spherical in shape as can be known, and the reunion degree is light, can be observed granularity and is about 6～7nm, with the D that calculates
110=6.1nm is substantially near (seeing Table 1).
Presoma uses fast quantification filter paper, and decompress filter washs isolating experimental result and sees Table 2:
Table 2 decompress filter separates presoma Sn (OH)
4, Sb (OH)
5
| Reaction system (suction filtration volume: 135mL) | Suction filtration required time (min) | Wash result (AgNO 3Detection has or not Cl -) | |
| 1. as the experiment technological process, after the complete reaction, decompress filter separates presoma, uses deionized water wash | For the first time | 6 | Cl is arranged - |
| For the second time | 15 | ||
| For the third time | Speed is very slow, can't separate | ||
| 2. as the experiment technological process, react completely, behind twice of deionized water wash, the ethanol that in washings subsequently, adds 10% (volume), decompress filter | For the first time | 6 | No Cl - |
| For the second time | 15 | ||
| For the third time | 6 | ||
| The 4th time | 3 | ||
| 3. as the experiment technological process, react completely, behind twice of deionized water wash, the ethanol that in washings subsequently, adds 15% (volume), decompress filter | For the first time | 6 | No Cl - |
| For the second time | 15 | ||
| For the third time | 4 | ||
| The 4th time | 2 | ||
| 4. as the experiment technological process, react completely, behind twice of deionized water wash, the acetone that in washings subsequently, adds 10% (volume), decompress filter | For the first time | 6 | No Cl - |
| For the second time | 15 | ||
| For the third time | 10 | ||
| The 4th time | 6 |
As shown in Table 2, if in washing separates the process of presoma, wash the suction filtration velocity of separation when being lower than 9ml/min (135mL/15min), the ethanol or the acetone solvent of adding 10% can make separation finish at short notice in washings subsequently, and adding ethanol effect is better.This method is continuously, batch process Sb
2O
5Adulterated nano SnO
2Created condition.
Claims (1)
1, a kind of oxidation and coprecipitation prepares the method for Sb-doped nano tin dioxide, may further comprise the steps: under (1) mechanical stirring, with SnCl
4And SbCl
3Mixing solutions, H
2O
2Solution and ammonia soln, under temperature of reaction, splash in the solution that contains anti-agglomeration agent-polyoxyethylene glycol, control entire reaction course PH, after reaction is finished, obtain containing the colloidal solution of presoma, (2) the presoma colloidal solution of gained obtains dry purified presoma Sn (OH) after centrifugation, washing, dehydration, vacuum-drying
4, Sb (OH)
5, (3) dry purified presoma Sn (OH)
4, Sb (OH)
5Behind the porphyrize, under differing temps, calcine, promptly get different big or small Nanometer-sized Antimony-doped tindioxide powders at last, it is characterized in that: 1. separate presoma Sn (OH) in washing
4, Sb (OH)
5Process in, at first use deionization washing, when washing the suction filtration velocity of separation when being lower than 9ml/min, the volumn concentration that contains that re-uses the deionized water preparation is that 6-20% ethanol or acetone or polyoxyethylene glycol washings are washed no Cl
-Till, 2. oxidation and coprecipitation prepares Sb-doped nano SnO
2Reaction conditions be: keep SnCl
4And SbCl
3Mixing solutions in SnCl
4Concentration be 2moll
-1, temperature of reaction is a room temperature to 50 ℃, and the molecular weight of polyoxyethylene glycol is 6000, and the control of PH adopts and splash into the excess of ammonia aqueous solution, form buffered soln controls, and calcining temperature is not less than 420 ℃.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB021354421A CN1171796C (en) | 2002-08-28 | 2002-08-28 | Oxidation and coprecipitation process of preparing Sb-doped nano tin dioxide |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB021354421A CN1171796C (en) | 2002-08-28 | 2002-08-28 | Oxidation and coprecipitation process of preparing Sb-doped nano tin dioxide |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1398791A CN1398791A (en) | 2003-02-26 |
| CN1171796C true CN1171796C (en) | 2004-10-20 |
Family
ID=4748201
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB021354421A Expired - Fee Related CN1171796C (en) | 2002-08-28 | 2002-08-28 | Oxidation and coprecipitation process of preparing Sb-doped nano tin dioxide |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1171796C (en) |
Families Citing this family (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100383518C (en) * | 2004-11-05 | 2008-04-23 | 广州大学 | Tin dioxide based nano gas sensitive material and preparation method thereof |
| CN100398450C (en) * | 2004-12-09 | 2008-07-02 | 中南大学 | Method of directly preparing high purity tin and antimony compeund fer ATO |
| CN100360424C (en) * | 2005-07-01 | 2008-01-09 | 中南大学 | Method for preparing nano antimony-doped tin dioxide powder |
| CN100537084C (en) * | 2007-12-21 | 2009-09-09 | 华中科技大学 | Process for producing Mn doping SnO2 room temperature diluted magnetic semiconductor nano-powder |
| JP5362734B2 (en) | 2008-10-24 | 2013-12-11 | 株式会社日清製粉グループ本社 | Powder classification method |
| CN102702518B (en) * | 2012-06-28 | 2013-09-11 | 山东大学 | Method for preparing composite material of stannic oxide/polyaniline |
| CN103626222B (en) * | 2013-11-15 | 2015-10-28 | 广东光华科技股份有限公司 | A kind of preparation method of micron order tin dioxide powder |
| CN104004387B (en) * | 2014-06-17 | 2016-04-13 | 安徽工业大学 | A kind of silicate powder of ATO nanoparticle parcel and application thereof |
| CN104150528B (en) * | 2014-08-28 | 2016-10-05 | 攀枝花学院 | A kind of preparation method of doping stannic oxide conducting nano powder |
| CA3017676C (en) * | 2016-03-18 | 2024-02-27 | Basf Se | Metal-doped tin oxide for electrocatalysis applications |
| CN114011407A (en) * | 2022-01-04 | 2022-02-08 | 天津市职业大学 | Photocatalytic material for treating oil field wastewater and preparation method and application thereof |
-
2002
- 2002-08-28 CN CNB021354421A patent/CN1171796C/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| CN1398791A (en) | 2003-02-26 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Nejati et al. | Synthesis of ZnO nanoparticles and investigation of the ionic template effect on their size and shape | |
| CN1171796C (en) | Oxidation and coprecipitation process of preparing Sb-doped nano tin dioxide | |
| CN1297484C (en) | Process for preparing one-dimensional nano tin dioxide material | |
| Rochman et al. | Fabrication and characterization of Zinc Oxide (ZnO) nanoparticle by sol-gel method | |
| CN1242342A (en) | Method for prodn. of mono-dispersed and crystalline TiO2 ultrafine powders from aqueous Tiocl2 solution using homogeneous precipitation | |
| Farrukh et al. | Influence of reaction parameters on the synthesis of surfactant-assisted tin oxide nanoparticles | |
| Sun et al. | Controllable synthesis and morphology-dependent photocatalytic performance of anatase TiO 2 nanoplates | |
| CN1226511A (en) | Method for preparing nano sized titanium dioxide powder by alcoholysis from titanic chloride | |
| CN1792812A (en) | Process for synthesizing spinel zine stannate nano rod | |
| Fernández et al. | Wet-chemical preparation of TiO2-nanostructures using different solvents: Effect of CTAB concentration and tentative mechanism of particle formation | |
| Divya et al. | Synthesis and characterization of branchlet-like SrCO3 nanorods using triethylamine as a capping agent by wet chemical method | |
| CN1568703A (en) | Attapulgite-argentum nanometer composite antibiotic material and preparation method thereof | |
| CN1613777A (en) | Preparation for nanometer anhydrous wolframic acid powder | |
| CN1071712C (en) | Method for preparing nanometre-grade zinc oxide | |
| CN1746130A (en) | Nanometer gas-sensing material of ternary composite metal oxide and production thereof | |
| Darezereshki et al. | Chemical process of synthesizing zinc oxide (ZnO) with nanorod and spherical morphologies | |
| Latifi et al. | Rice-like Ag/Al 2 O 3 nanocomposites preparation from AlOOH nanostructures synthesized via a facile hydrothermal route for azo dyes photocatalytic degradation and Pb 2+ adsorption | |
| Abla et al. | Exceptionally redox-active precursors in the synthesis of gold core-tin oxide shell nanostructures | |
| Athar | Metal oxide nanopowder | |
| Lee et al. | Synthesis of fine sodium-free silica powder from sodium silicate using w/o emulsion | |
| Siahpoosh et al. | Synthesis of γ-Alumina nanoparticles with high-surface-area via Sol-Gel method and their performance for the removal of Nickel from aqueous solution | |
| CN108946796B (en) | Doped titanate and preparation method thereof | |
| CN1872917A (en) | In situ method for preparing modified Nano powder of hydrate, hydroxy salt, and oxide | |
| Ban et al. | Hydrothermal synthesis of highly water-dispersible anatase nanocrystals from transparent aqueous sols of titanate colloids | |
| CN1626446A (en) | Method for preparing Nano zinc oxide material in controllable size |
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 | ||
| C19 | Lapse of patent right due to non-payment of the annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |