CN102774882B - Method for preparing candied haw-shaped pure anatase type nano-titania wire in larger scale - Google Patents
Method for preparing candied haw-shaped pure anatase type nano-titania wire in larger scale Download PDFInfo
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- CN102774882B CN102774882B CN 201210231822 CN201210231822A CN102774882B CN 102774882 B CN102774882 B CN 102774882B CN 201210231822 CN201210231822 CN 201210231822 CN 201210231822 A CN201210231822 A CN 201210231822A CN 102774882 B CN102774882 B CN 102774882B
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Abstract
The invention relates to a method for preparing a candied haw-shaped pure anatase type nano-titania wire in a large scale, which is that a titanic acid nanowire is washed to be neutral, is put in a muffle to be heated at a heating rate of 2-5 DEG C/min, and is thermally insulated for 2-3 hours at the temperature of 650-800 DEG C, and accordingly, the required nano-titania wire is obtained. The method has a simple technology and is suitable for mass production; and the obtained nano-titania wire is of a candied haw shape, has good dispersity, larger slender proportion and large specific surface area, and is easy for settling separation, so the problems of separating and recovering titanium dioxide particles in the solution are solved.
Description
Technical field
The present invention relates generally to a large amount of preparation methods of the pure anatase-type nanometer titanium dioxide line of a kind of sugarcoated haws on a stick shape.
Background technology
After Fujishima in 1972 and Honda find titanium dioxide photodissociation water, because titanium dioxide is with a wide range of applications at aspects such as solar cell, photochemical catalysis, photodissociation water and sensor batteries, become the focus of material subject research.
In recent years, one-dimensional titanium dioxide nanostructure (nanotube, nanometer rod, nano wire) replaces the focus that titania nanoparticles becomes research, this is because photo-generated carrier can be in the axial long Distance Transmission of one dimension Nano structure, reduced the probability of hole and electron recombination, efficiency when expection can improve its photochemical catalysis, photodissociation water, solar cell.The titanium dioxide nano material of while one dimension is compared titanium dioxide granule and is had characteristics easily separated and that easily reclaim in photodissociation water.
Up to the present, report the multiple method for preparing one-dimensional titanium dioxide nanostructure, comprised chemical Vapor deposition process, template, titanium plate anonizing, electrical spinning method and titanate transformation approach etc.In these methods, the titanate transformation approach, because its cost is low and easily a large amount of preparations, is hopeful to realize industrial applications most.But many preparation methods do not obtain desirable pure anatase titanium dioxide nanostructure, do not obtain in shape sugarcoated haws on a stick shape nano wire at nano wire in addition.
As patent of invention CN100427404C has confirmed the limitation in the one-dimensional titanium dioxide preparation method of nano material in CN1699636A by experiment, and point out that titanyl powder and strong lye thermal response product are the sodium titanate nano wire, it after pickling, is the metatitanic acid nano wire, rather than document is said in the past anatase octahedrite or red schorl phase titanium dioxide nano line (pipe), and confirmed this point with experiment.The inventor has also done example laboratory, the results are shown in Figure the electromicroscopic photograph of 2(metatitanic acid nano wire), Fig. 3 (the X diffraction picture of metatitanic acid nano wire), not as the anatase phase titanium dioxide nano wire of saying in relevant patent and document.
Summary of the invention
The technical problem to be solved in the present invention is that a kind of technique of searching is simple, is applicable to the method for the pure anatase-type nanometer titanium dioxide line of scale operation sugarcoated haws on a stick shape.The present invention chooses suitable calcining temperature, temperature rise rate and soaking time, and the metatitanic acid nano wire is converted to sugarcoated haws on a stick shape anatase titanium dioxide nano wire fully.
After the present invention washs into neutrality by the metatitanic acid nano wire, insert the temperature rise rate with 2-5 ℃/min in retort furnace and heat, and be incubated 2-3 hour at the temperature of 650-800 ℃, thereby obtain needed titanium dioxide nano thread.
The preparation method of described metatitanic acid nano wire is: the titanyl powder adds aqueous sodium hydroxide solution, by hydro-thermal reaction, obtains the sodium titanate nano wire; Wash with water and obtain the sodium titanate nano wire; Sodium titanate nano wire after washing is joined in the acid solution of PH=1-2 and carries out ion-exchange, obtain the metatitanic acid nano wire.
Required titanyl powder is titanium dioxide, metatitanic acid, meta-titanium perborate or their combination.
Wherein hydrothermal temperature is 160-250 ℃. the reaction times is 1-7d.
Naoh concentration is 5-15mol/L.
The pickling concentration PH1-2 of sodium titanate nano wire, the kind of acid can be hydrochloric acid, sulfuric acid or nitric acid.
The present invention, by choosing suitable calcining temperature and temperature rise rate and soaking time, is converted to the anatase titanium dioxide nano wire fully by the metatitanic acid nano wire, and the major advantage of the pure anatase-type nanometer titanium dioxide line of gained sugarcoated haws on a stick shape is:
1. preparation technology is simple, and parameter is easy to control, is applicable to extensive preparation.
2. resulting anatase titania nano wire is the sugarcoated haws on a stick shape, and good dispersity has larger slenderness ratio, large specific surface area, and free settling separates, and has solved the problem of titanium dioxide granule Separation and Recovery in solution.
3. to have a production cost low for titanium dioxide of the present invention, can be recycled, and aspect the water treatment organic matter degradation, is being with a wide range of applications.
The accompanying drawing explanation
Fig. 1 is the metatitanic acid nano wire electromicroscopic photograph prepared with reference to CN1699636A
Fig. 2 is the metatitanic acid nano wire X ray picture prepared with reference to CN1699636A
Fig. 3 is the titanium dioxide nano thread electromicroscopic photograph of the embodiment of the present invention 1 preparation
Fig. 4 is the titanium dioxide nano thread X ray picture of the embodiment of the present invention 1 preparation
Fig. 5 is the titanium dioxide nano thread electromicroscopic photograph of the embodiment of the present invention 2 preparations
Fig. 6 is the titanium dioxide nano thread X ray picture of the embodiment of the present invention 2 preparations
Fig. 7 is the titanium dioxide nano thread X ray picture of Comparative Examples 1 preparation of the present invention
Fig. 8 is Comparative Examples 1(600 ℃ of the present invention) the titanium dioxide nano thread electromicroscopic photograph for preparing
Fig. 9 is Comparative Examples 1(850 ℃ of the present invention) the titanium dioxide nano thread electromicroscopic photograph for preparing
The specific examples mode
Embodiment 1
The 30ml5MNaOH solution that injection prepares in advance in the autoclave (inner liner polytetrafluoroethylene 316 stainless steels) of 50mL, then add 0.2gTiO
2nanometer powder ((P25, Degussa), the ultrasonic TiO that makes
2powder is uniformly dispersed, then the sealing, in the furnace temperature of 160 ℃ (thermostatic drying chamber), hydro-thermal reaction is 24 hours, cooling after, go supernatant liquor can make white depositions, include self-growing sodium titanate nano wire.First will be rich in sodium titanate nano wire white depositions and successively use distilled water, dilute hydrochloric acid (pH=2), distilled water repetitive scrubbing, until neutral, generate the metatitanic acid nano wire.After filtering collection, put in retort furnace and calcine, heating gradient is respectively 2-5 ℃/min, and in the stove of 650 ℃, heat preservation hot is processed 2h, obtains required sample.
Embodiment 2
The 300ml15MNaOH solution that injection prepares in advance in the autoclave (inner liner polytetrafluoroethylene 316 stainless steels) of 500mL, then add 6gTiO
2nanometer powder ((P25, Degussa), the ultrasonic TiO that makes
2powder is uniformly dispersed, then the sealing, in the furnace temperature of 250 ℃ (thermostatic drying chamber), hydro-thermal reaction is 7 days, cooling after, go supernatant liquor can make white depositions, include self-growing sodium titanate nano wire.First will be rich in sodium titanate nano wire white depositions and successively use distilled water, dilute hydrochloric acid (pH=1), distilled water repetitive scrubbing, until neutral, generate the metatitanic acid nano wire.After filtering collection, put in retort furnace and calcine, heating gradient is respectively 2-5 ℃/min, and in the stove of 800 ℃, heat preservation hot is processed 2h, obtains required sample.
It is 35.2m that embodiment 1,2 all can obtain specific surface area
2/ g, length is at tens microns, and diameter is at the sugarcoated haws on a stick shape nano wire of 20 nanometer left and right, and dispersing property is good, and free settling separates.
Comparative Examples
The 30ml5MNaOH solution that injection prepares in advance in the autoclave (inner liner polytetrafluoroethylene 316 stainless steels) of 50mL, then add 0.2gTiO
2nanometer powder ((P25, Degussa), the ultrasonic TiO that makes
2powder is uniformly dispersed, then the sealing, in the furnace temperature of 160 ℃ (thermostatic drying chamber), hydro-thermal reaction is 24 hours, cooling after, go supernatant liquor can make white depositions, include self-growing sodium titanate nano wire.First will be rich in sodium titanate nano wire white depositions and successively use distilled water, dilute hydrochloric acid (pH=2), distilled water repetitive scrubbing, until neutral, generate the metatitanic acid nano wire.After filter collecting, put in retort furnace and calcine, heating gradient is respectively 2-5 ℃/min, and respectively in the stove of 645 ℃, 805 ℃ heat preservation hot process 2h, obtain required sample.Result shows that 645 ℃ of continuous thermal treatment temps change without obvious crystalline phase, has occurred rutile phase in the time of 805 ℃, be not pure Anatase, so subsequent heat treatment all adopts 650 ℃ ~ 800 ℃.Sugarcoated haws on a stick shape nano wire does not appear in the SEM picture of 645 ℃ of thermal treatment temps in addition, and the SEM picture that thermal treatment temp is 805 ℃ is sugarcoated haws on a stick shape nano wire, but it rutile phase occurred, is not pure Anatase.
Other preparation methods are with embodiment 1, and when heating gradient is 1.5 ℃/min, rutile phase has appearred in products obtained therefrom, are not pure Anatases, when heating gradient is 5.5 ℃/min, sugarcoated haws on a stick shape nano wire do not occur.
The above-mentioned foundation desirable embodiment of the present invention of take is enlightenment, and by above-mentioned description, the relevant staff can, in the scope that does not depart from this invention technological thought, carry out various change and modification fully.The technical scope of this invention is not limited to the content on specification sheets, must determine its technical scope according to the claim scope.
Claims (4)
1. a large amount of preparation methods of the pure anatase-type nanometer titanium dioxide line of sugarcoated haws on a stick shape: the titanyl powder adds aqueous sodium hydroxide solution, by hydro-thermal reaction, obtains the sodium titanate nano wire; Wash with water and obtain the sodium titanate nano wire; Sodium titanate nano wire after washing is joined in the acid solution of PH=1-2 and carries out ion-exchange, obtain the metatitanic acid nano wire; After the sodium titanate nano wire is washed into to neutrality, insert the temperature rise rate with 2-5 ℃/min in retort furnace and heat, and be incubated 2-3 hour at the temperature of 650-800 ℃, thereby obtain needed titanium dioxide nano thread.
2. a large amount of preparation methods of the pure anatase-type nanometer titanium dioxide line of the described sugarcoated haws on a stick shape of claim 1, is characterized in that required titanyl powder is titanium dioxide, metatitanic acid, meta-titanium perborate or their combination.
3. a large amount of preparation methods of the pure anatase-type nanometer titanium dioxide line of the described sugarcoated haws on a stick shape of claim 1, is characterized in that hydrothermal temperature is 160-250 ℃. the reaction times is 1-7d.
4. a large amount of preparation methods of the pure anatase-type nanometer titanium dioxide line of the described sugarcoated haws on a stick shape of claim 1, is characterized in that naoh concentration is 5-15mol/L.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100427404C (en) * | 2006-07-27 | 2008-10-22 | 北京先讯东泰科技有限公司 | Method for preparing Nano line of titania, and application of the prepared Nano line of titania |
| JP2008297147A (en) * | 2007-05-30 | 2008-12-11 | Hokkaido Univ | Production method of anatase octahedral titanium oxide fine particle and titanium oxide fine particles |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100427404C (en) * | 2006-07-27 | 2008-10-22 | 北京先讯东泰科技有限公司 | Method for preparing Nano line of titania, and application of the prepared Nano line of titania |
| JP2008297147A (en) * | 2007-05-30 | 2008-12-11 | Hokkaido Univ | Production method of anatase octahedral titanium oxide fine particle and titanium oxide fine particles |
Non-Patent Citations (2)
| Title |
|---|
| 二氧化钛纳米材料的晶型与形貌调控及光催化活性研究;沈晓军;《中国博士学位论文全文数据库》;20120428;第114-115、117页 * |
| 沈晓军.二氧化钛纳米材料的晶型与形貌调控及光催化活性研究.《中国博士学位论文全文数据库》.2012,第114-115、117页. |
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Effective date of registration: 20201223 Address after: 321 provincial road, Jinlong Village, Zhongming Town, Yi'an District, Tongling City, Anhui Province Patentee after: Tongling Xinlong Steel Structure Co.,Ltd. Address before: Gehu Lake Road Wujin District 213164 Jiangsu city of Changzhou province No. 1 Patentee before: CHANGZHOU University |