CN102432064A - Method for synthesizing nanometer titanium dioxide by reverse microemulsion carbon adsorption titanium tetrachloride hydrolytic system - Google Patents
Method for synthesizing nanometer titanium dioxide by reverse microemulsion carbon adsorption titanium tetrachloride hydrolytic system Download PDFInfo
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- CN102432064A CN102432064A CN2011102793381A CN201110279338A CN102432064A CN 102432064 A CN102432064 A CN 102432064A CN 2011102793381 A CN2011102793381 A CN 2011102793381A CN 201110279338 A CN201110279338 A CN 201110279338A CN 102432064 A CN102432064 A CN 102432064A
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- titanium tetrachloride
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Abstract
The invention relates to a method for synthesizing nanometer titanium dioxide by reverse microemulsion carbon adsorption titanium tetrachloride hydrolytic system, belongs to the field of nano material preparation technology. The invention solves the problems of easy agglomeration and sintering of ultrafine titanium dioxide. The method is comprises the following steps: adopting titanium tetrachloride, carbon black, and acetic acid as raw materials, preparing a cyclohexane microemulsion system by an acetic acid aqueous solution with a pH of 2, dropwisely adding into a cyclohexane microemulsion system formed by titanium tetrachloride, anhydrous alcohol, and carbon black, mixing and stirring at normal temperature, pouring into a reaction kettle, reacting in the microreactor by hydrothermal reaction, reduced-pressure distillation, washing, drying, grinding, and calcining the precipitates adsorbed by the carbon black, obtaining the nanometer titanium dioxide with high-temperature stability. The invention has mild reaction conditions, high yield; the obtained product has high crystallinity, large specific surface area, small particle size, good photocatalytic activity.
Description
Technical field
The present invention relates to reverse micro emulsion charcoal absorption titanium tetrachloride hydrolysis system nano titanium oxide synthetic method, belong to the nano material preparation technical field.
Background technology
Photochemical catalysis is a kind of emerging environmental purification technology.Nano titanium dioxide photocatalysis oxidation or reduction effectively is adsorbed on its lip-deep harmful molecule, and kill bacteria suppresses virus, and can harmful organic substance, bacterium etc. be converted into innoxious substances such as water and carbonic acid gas, and has no secondary pollution.The photocatalyst of existing preparation is nano TiO 2 powder mostly; In order to improve the photocatalytic activity of titanium oxide; Must make it have higher percent crystallinity, smaller particles size and higher specific surface area,, increase active so that there is more chain carrier to participate in reaction.Prepared by reverse microemulsion method titanium oxide nanoparticles at present commonly used, this method be mainly with the water nuclear of the w/o type microemulsion microreactor as precipitin reaction, will contain to remain the microemulsion of precipitating ion and mix with the another kind of microemulsion that contains precipitation agent.The certain concentration gradient of the unavoidable generation of mixing process causes the process of different zones precipitin reaction in the microemulsion asynchronous, and the synthetic nano particle diameter distributes and broadens.The titanium oxide ultra-fine grain that makes all is easy to generate reunion, sintering in dry, roasting stage, and the particle diameter of synthetic nanoparticle increases.As how simple preparation method obtains uniform particles, crystal formation is good, specific surface area is big ultrafine titania and avoids in reunion dry, heat treatment stages, is the target that people seek for a long time.
Summary of the invention
The present invention provides a kind of can stop reunion and the agglomerating reverse micro emulsion charcoal absorption titanium tetrachloride hydrolysis system nano titanium oxide synthetic method of titanium oxide in the preparation process.
Technical solution:
The present invention includes the method for being prepared as follows:
(1) be to measure titanium tetrachloride and absolute ethyl alcohol in ice-water bath stir at 0.5～1.5: 20 by volume, mixed system A;
(2) the cetyl trimethylammonium bromide CTAB of 0.50～0.7g is dissolved in the 200mL hexanaphthene makes solution B; Measure 5mL mixed system A, add in the solution B, stir; To system is that achromaticity and clarification is stablized microemulsion C; Be 0.50～0.85: 1 ratio weighing carbon black again in contained titanium tetrachloride mass ratio among carbon black and the microemulsion C, carbon black is added solution C, continue in ice-water bath, to stir, ultrasonic oscillation 1～2h gets mixed system D;
(3) 0.50～0.7g cetyl trimethylammonium bromide CTAB is dissolved in the 200mL hexanaphthene, the pH value that drips the configuration of use acetic acid is 1～2 aqueous acetic acid 2.5ml, drips 6～8ml propyl carbinol simultaneously, stir, and be that achromaticity and clarification is stablized microemulsion E to system;
(4) mixed system D is mixed with microemulsion E, stir 20～40min, pour into then in the teflon-lined autoclave; Temperature: 120 ℃～160 ℃; Stir 8～14h postcooling to room temperature, gained charcoal adsorption precipitation thing is used deionized water wash, dry 3～5h under 80～100 ℃ condition; Heat-up rate with 10～20 ℃/min after grinding is warming up to 500～800 ℃ of roasting 2～4h, gets the high thermal stability nano titanium oxide.
Said acetic acid is Glacial acetic acid min. 99.5.
Using Glacial acetic acid min. 99.5 to transfer to pH value of aqueous solution is 2.
The present invention adds the another kind of microemulsion that contains precipitation agent then and mixes the Ti of formation (OH) owing in treating the microemulsion of precipitating ion, add suitable carbon black
4Fine powder is adsorbed by carbon black, has stoped ultra-fine grain to produce at deposition, drying stage on the one hand and has reunited.On the other hand, when dried mixture is elevated to 300 ℃ when temperature, Ti (OH)
4Powder decomposition formation TiO
2Nano-powder, this moment, carbon was not oxidized, had prevented TiO
2Nano-powder is at the sintering in roasting stage.TiO
2Nano-powder is actually the product that microemulsion and adsorbing coupled " wetting " process of carbon combine with " doing " process; Be expected to synthesize the particle that has than small particle size and concentrate size distribution, prepare the reunion and the sintering problem of Nano titanium dioxide for solution utilizes the microemulsion method.
In a single day effect of the present invention: the present invention adds an amount of carbon black in microemulsion, as strong sorbent material, in microreactor, forms nano particle, by carbon black absorption, stoped ultra-fine grain in deposition, dry, roasting stage generation reunion.Thermal treatment does not see that rutile produces mutually under 800 ℃ of hot conditionss, explains and adopts the reverse micro emulsion carbon adsorption can significantly improve the transition temperature of anatase titanium dioxide, thereby improve its thermostability; 500 ℃ of roasting 2h charcoal absorption nano titanium oxide specific surface areas are 78.6m
2/ g, about 18 nanometers of particle diameter are about 50m with degussa vapor phase process synthetic specific surface area
2/ g nano titanium oxide (TiO
2P25) compare, specific surface area increases about 28m
2/ g.Adopt the carbon adsorption production cost low, be convenient to carry out the production of extensive nano titanium oxide.
Reaction conditions of the present invention is gentle, productive rate is high; The product percent crystallinity that obtains is high, and specific surface area is big, and particle diameter is little, and photocatalysis performance is good.
Description of drawings
Fig. 1 is the XRD spectra of specific embodiment of the invention gained charcoal absorption titanium oxide sample behind 800 ℃ of maturing temperature sintering;
Fig. 2 is 500 ℃ of SEM figure behind the sintering for specific embodiment of the invention gained charcoal absorption titanium oxide sample through maturing temperature.
Embodiment
Embodiment
(1) gets titanium tetrachloride 1.85ml and absolute ethyl alcohol 37ml, titanium tetrachloride and raw spirit magnetic agitation, the common 1h of ultrasonic oscillation in ice-water bath are got mixed solution A;
(2) cetyl trimethylammonium bromide (CTAB) of 0.60g is dissolved in the 200mL hexanaphthene makes solution B; The mixing solutions 5mL that step (1) is prepared slowly adds in the solution B; Stir; Transfer achromaticity and clarification to system to by the opaque milk sap of oyster white and stablize microemulsion, the 0.31g carbon black is added in the solution B, continuation is stirred in ice-water bath, ultrasonic oscillation is total to 2h and gets mixed system C;
(3) 0.60g cetyl trimethylammonium bromide (CTAB) is dissolved in the 200mL hexanaphthene; PH value that drip to use the acetic acid configuration is 2 aqueous acetic acid 2.5ml, drips propyl carbinol 7ml simultaneously and transfers achromaticity and clarification to system to by the opaque milk sap of oyster white and stablize microemulsion D;
(4) mixed system C is mixed with microemulsion D; Stir 20～40min, pour into then in the teflon-lined autoclave, at 150 ℃; Stir hydro-thermal 10h postcooling to room temperature down; Gained charcoal adsorption precipitation thing is after repeatedly washing, and the heat-up rate with 10 ℃/min is warming up to 500 ℃ or 800 ℃ of roasting 4h after dry and grinding again, gets the high thermal stability nano titanium oxide.
Comparative example: as comparing, we utilize degussa vapor phase process synthetic nano titanium oxide (TiO
2P25) compare; The nano titanium oxide that the present invention makes can be known by Fig. 1, and thermal treatment does not see that rutile produces mutually under 800 ℃ of hot conditionss; Explain and adopt the reverse micro emulsion carbon adsorption can significantly improve the transition temperature of anatase titanium dioxide, thereby improve its thermostability; 500 ℃ of roasting 2h charcoal absorption nano titanium oxide specific surface areas are 78.6m
2/ g, about 18 nanometers of particle diameter are about 50m with degussa vapor phase process synthetic specific surface area
2/ g nano titanium oxide (TiO
2P25) compare, specific surface area increases about 28m
2/ g.Simultaneously, can know by Fig. 2, the nano titanium oxide that the present invention makes, percent crystallinity is high, and specific surface area is big, and particle diameter is little, adopts the carbon adsorption production cost low, is convenient to carry out the production of extensive nano titanium oxide.
Claims (3)
1. the reverse micro emulsion charcoal adsorbs titanium tetrachloride hydrolysis system nano titanium oxide synthetic method, it is characterized in that method steps is following:
(1) be to measure titanium tetrachloride and absolute ethyl alcohol in ice-water bath stir at 0.5～1.5: 20 by volume, mixed system A;
(2) the cetyl trimethylammonium bromide CTAB of 0.50～0.7g is dissolved in the 200mL hexanaphthene makes solution B; Measure 5mL mixed system A, add in the solution B, stir; To system is that microemulsion C is stablized in clarification; Be 0.50～0.85: 1 ratio weighing carbon black again in contained titanium tetrachloride mass ratio among carbon black and the microemulsion C, carbon black is added solution C, continue in ice-water bath, to stir, ultrasonic oscillation 1～2h gets mixed system D;
(3) 0.50～0.7g cetyl trimethylammonium bromide CTAB is dissolved in the 200mL hexanaphthene, the pH value that drips the configuration of use acetic acid is 1～2 aqueous acetic acid 2.5ml, drips 6～8ml propyl carbinol simultaneously, stir, and be that microemulsion E is stablized in clarification to system;
(4) mixed system D is mixed with microemulsion E, stir 20～40min, pour into then in the teflon-lined autoclave; Temperature: 120 ℃～160 ℃; Stir 8～14h postcooling to room temperature, gained charcoal adsorption precipitation thing is used deionized water wash, dry 3～5h under 80～100 ℃ condition; Heat-up rate with 10～20 ℃/min after grinding is warming up to 500～800 ℃ of roasting 2～4h, gets the high thermal stability nano titanium oxide.
2. reverse micro emulsion charcoal absorption titanium tetrachloride hydrolysis system nano titanium oxide synthetic method according to claim 1 is characterized in that said acetic acid is Glacial acetic acid min. 99.5.
3. reverse micro emulsion charcoal absorption titanium tetrachloride hydrolysis system nano titanium oxide synthetic method according to claim 1 is characterized in that using Glacial acetic acid min. 99.5 to transfer to pH value of aqueous solution is 2.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102838159A (en) * | 2012-09-26 | 2012-12-26 | 内蒙古科技大学 | Method for synthesizing nano-zinc oxide by micro-emulsion carbon black adsorption precipitation method |
| CN105983273A (en) * | 2015-02-17 | 2016-10-05 | 刘朝南 | Active suspension filtering material and preparation method thereof |
| CN108975391A (en) * | 2018-07-26 | 2018-12-11 | 四川理工学院 | A kind of synthetic method of metal oxide nano microballoon |
| CN109721368A (en) * | 2019-03-12 | 2019-05-07 | 厦门理工学院 | A kind of method that carbon titanium carbonitride powder and hydrolyzable titanium source prepare titanium carbonitride |
| CN113135591A (en) * | 2021-03-24 | 2021-07-20 | 湖北文理学院 | Preparation method of titanium dioxide nanorod array |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101333002A (en) * | 2007-06-27 | 2008-12-31 | 中国科学院合肥物质科学研究院 | Titanium dioxide nanometer powder with special appearance and method for preparing same |
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Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101333002A (en) * | 2007-06-27 | 2008-12-31 | 中国科学院合肥物质科学研究院 | Titanium dioxide nanometer powder with special appearance and method for preparing same |
Non-Patent Citations (3)
| Title |
|---|
| LIN, PING等: "Synthesis and characterization of titania nanoparticles by microemulsion process", 《INDIAN JOURNAL OF CHEMISTRY SECTION A-INORGANIC BIO-INORGANIC PHYSICAL THEORETICAL & ANALYTICAL CHEMISTRY》, vol. 45, no. 9, 30 September 2006 (2006-09-30), pages 2017 - 2020 * |
| 郭贵宝等: "均匀沉淀和碳吸附耦合法制备CeO2纳米粒子及表征", 《应用化学》, vol. 23, no. 6, 30 June 2006 (2006-06-30), pages 622 - 625 * |
| 黄永兰: "反相微乳液法制备纳米TiO2", 《化学工程师》, no. 9, 31 December 2010 (2010-12-31), pages 53 - 56 * |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102838159A (en) * | 2012-09-26 | 2012-12-26 | 内蒙古科技大学 | Method for synthesizing nano-zinc oxide by micro-emulsion carbon black adsorption precipitation method |
| CN105983273A (en) * | 2015-02-17 | 2016-10-05 | 刘朝南 | Active suspension filtering material and preparation method thereof |
| CN105983273B (en) * | 2015-02-17 | 2018-05-01 | 刘朝南 | A kind of activity suspended filter material and preparation method thereof |
| CN108975391A (en) * | 2018-07-26 | 2018-12-11 | 四川理工学院 | A kind of synthetic method of metal oxide nano microballoon |
| CN108975391B (en) * | 2018-07-26 | 2020-06-02 | 四川理工学院 | Synthesis method of metal oxide nano-microspheres |
| CN109721368A (en) * | 2019-03-12 | 2019-05-07 | 厦门理工学院 | A kind of method that carbon titanium carbonitride powder and hydrolyzable titanium source prepare titanium carbonitride |
| CN109721368B (en) * | 2019-03-12 | 2021-06-25 | 厦门理工学院 | Titanium carbonitride powder and method for preparing titanium carbonitride from hydrolyzable titanium source |
| CN113135591A (en) * | 2021-03-24 | 2021-07-20 | 湖北文理学院 | Preparation method of titanium dioxide nanorod array |
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