CN101302036A - Preparation of doped titanium dioxide nano-tube - Google Patents
Preparation of doped titanium dioxide nano-tube Download PDFInfo
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- CN101302036A CN101302036A CNA2008100537374A CN200810053737A CN101302036A CN 101302036 A CN101302036 A CN 101302036A CN A2008100537374 A CNA2008100537374 A CN A2008100537374A CN 200810053737 A CN200810053737 A CN 200810053737A CN 101302036 A CN101302036 A CN 101302036A
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- titanium dioxide
- doped
- adulterated
- nanotube
- titania nanoparticles
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Abstract
The invention discloses a method for preparing a nanotube doped with titanium dioxide by a two-step presynthesis method. Firstly, a sol-gel method or a hydrolysis method and other methods are adopted to synthesize nano particles doped with the titanium dioxide for target elements; secondly, the nano particles are made into the nanotube doped titanium dioxide by the hydrolysis method. The method has simple and feasible process, wide and application range for the doped elements; moreover, the nanotube prepared by the method has thin tube wall, small tube diameter, large surface area, response to visible light, and wide application prospect in aspects such as photocatalysis, photosensing, photoelectric conversion and so on.
Description
[technical field]
The present invention relates to a kind of preparation method of doped titanic oxide nano tube, belong to field of nanometer material technology.
[background technology]
Since having found that carbon nanotube has excellent properties such as toughness is strong, specific surface area is big, intensity height, people have launched the broad research to the nanotube of various materials.Simultaneously, because titanium dioxide has advantages such as cheap, good stability, titania nanotube is at organic matter degradation, opto-electronic conversion, photolysis water hydrogen, extremely World Science man concern of the application of aspects such as optical sensor.
But because the titanium dioxide energy gap is 3.2eV, can only absorbing wavelength less than the UV-light of 387nm, and major part is a visible light in the sunlight, the composition of UV-light only accounts for 5%.At present, low the becoming of sunlight utilization ratio hinders the subject matter that titanium dioxide is used.In recent years in order to improve the visible light utilization ratio of titanium dioxide, single-phase or heterogeneous doping and compound control technique are used for strengthening the absorption to visible light of titanium dioxide nano-particle or film by people.Simultaneously, the shallow energy level that doped element forms can become the trap center in light induced electron or hole, helps photo-generated carrier and separates, thereby improve photo-quantum efficiency.Calendar year 2001, professor R.Asahi etc. have prepared the adulterated high reactivity TiO of N
2Visible light catalyst has caused the upsurge of nonmetal doping.2006, In etc. prepared B, the active titanium deoxide catalyst of N codoped high visible.Other element doping titanium dioxide such as Sn, Fe, In, P, S, C have also attracted people's very big interest.But,, therefore fewer about the report of doping or composite nano pipe because preparation technology's more complicated of titania nanotube is not utilized doping or compound.
The present invention adopts pre-synthesis method of two steps: first synthesizing blender titania nanoparticles, again nano particle is made doped titanic oxide nano tube by hydrothermal method.This method simple possible, the nanotube tube wall of preparing is thin, and caliber is little, and specific surface area is big.But hydrothermal method is reacted titanium dioxide under strong alkali environment, is unfavorable for the existence of other dopant ions, and dopant ion also is not easy to enter the titanium dioxide lattice that has formed.Therefore, be the difficult problem that to capture with the visible light-responded dopen Nano pipe of hydro-thermal legal system always.
[summary of the invention]
Main purpose of the present invention is to prepare a kind of visible light-responded dopen Nano pipe that has.Adopt the pre-two step synthesis methods of mixing, concrete steps are as follows:
1. prepare adulterated nano titanium dioxide powder with methods such as sol-gel method or hydrolysis method.Doping should be bigger, and should make foreign atom enter the titanium dioxide lattice.
2. the preparation of titanate nanotube.Concentrated alkali solution and a certain amount of doped nano titanium dioxide powder are put into autoclave mix stirring 30min, be heated to then and react about 20h naturally cooling more than 100 ℃.
3. will obtain product and remove supernatant liquid after centrifugal, with deionized water to washing of precipitate to neutrality, soak about 30min with dilute hydrochloric acid, behind the recentrifuge precipitation is washed to neutrality.
4. with after the neutral products oven dry, put into retort furnace and calcined 2.5 hours down for 400 ℃, promptly get Detitanium-ore-type visible light-responsible titanium dioxide nanotube.
The nanotube that the present invention adopts pre-synthesis method of two steps to make has stronger visible absorption, and tube wall is thin, and specific surface area is big, and crystal formation is good, and doping is controlled, and this preparation method technology is simple, and easy handling is applicable to the doping of various elements.
[description of drawings]
N doped Ti O among Fig. 1 embodiment 1
2The transmission electron microscope of nanotube (TEM) picture.
The X-ray diffraction (XRD) of product figure is (with pure TiO among all embodiment of Fig. 2
2Relatively)
N doped Ti O among Fig. 3 embodiment 1
2The UV, visible light diffuse-reflectance of nanotube absorbs figure (with pure TiO
2Relatively)
[embodiment]
Embodiment 1:In doped Ti O
2Nanotube
1. adopt sol-gel method to prepare In doped Ti O
2Nanometer powder.Get the 12ml tetrabutyl titanate and slowly splash into and be mixed with the 40ml dehydrated alcohol, in the beaker of 2ml deionized water and 1ml hydrochloric acid, stir half an hour after, add the 0.2ml Indium-111 chloride and splash into beaker; Obtain vitreosol, leave standstill for some time, behind the gel,, obtain xerogel in 100 ℃ of freeze-day with constant temperature 10 ~ 12 hours; After the grinding, 450 ℃ of calcinings were taken out after 2.5 hours, obtained In doped Ti O
2Nanometer powder.
2. with 0.4g In doped Ti O
2Nanometer powder and 18ml 10mol/L NaOH solution mix and add reactor and stir, after half hour, place baking oven to be heated to 110 ℃ autoclave, insulation 20h.
3. the autoclave that will react takes out, treat naturally cooling after, centrifugal, outwell supernatant liquid, precipitate with deionized water is washed until neutrality, use 0.1mol/L salt acid soak half hour again, with deionized water product is washed neutrality once more afterwards.
4. products therefrom is tiled in the watch-glass, put into baking oven with 100 ℃ of baking 12h, the block that takes out after drying grinds gently.Product after grinding is put into retort furnace with 400 ℃ of sintering temperature 2.5h, and then after grinding gently once more, promptly make required TiO
2Nanotube.
Embodiment 2:N doped Ti O
2Nanotube
1. adopt TiCl
4Hydrolysis method prepares N doped Ti O
2Nanometer powder.25% ammoniacal liquor dropwise joins 200mL under vigorous stirring concentration is about 0.1molL
-1Titanium tetrachloride aqueous solution in, produce white precipitate in the system at once, when the pH of system value reaches 5.5, stop to add ammoniacal liquor.Still aging then 24h filters, and gained is deposited in 70 ℃ of oven dry, grind into powder, and 400 ℃ of sintering 4 hours.Promptly obtain N doped Ti O
2Nanometer powder
2. with 0.4g N doped Ti O
2Nanometer powder and 18ml 10mol/L NaOH solution mix and add reactor and stir, after half hour, place baking oven to be heated to 110 ℃ autoclave, insulation 20h.
3. the autoclave that will react takes out, treat naturally cooling after, centrifugal, outwell supernatant liquid, precipitate with deionized water is washed until neutrality, use 0.1mol/L salt acid soak half hour again, with deionized water product is washed neutrality once more afterwards.
4. products therefrom is tiled in the watch-glass, put into baking oven with 100 ℃ of baking 12h, the block that takes out after drying grinds gently.Product after grinding is put into retort furnace with 400 ℃ of sintering temperature 2.5h, and then after grinding gently once more, promptly make required TiO
2Nanotube.
Embodiment 3:N, Sn codope TiO
2Nanotube
1. adopt sol-gel method to prepare N, Sn codope TiO
2Nanometer powder.Getting the 12ml tetrabutyl titanate slowly splashes into and is mixed with the 40ml dehydrated alcohol, in the beaker of 2ml deionized water and 1ml hydrochloric acid, after stirring half an hour, add the 0.2ml tin tetrachloride, after half an hour, add 3ml ammoniacal liquor, obtain vitreosol, leave standstill for some time, behind the gel, in 100 ℃ of freeze-day with constant temperature 10 ~ 12 hours, obtain xerogel; After the grinding, 450 ℃ of calcinings were taken out after 2.5 hours, obtained N, Sn codope TiO
2Nanometer powder.
2. with 0.4g N, Sn codope TiO
2Nanometer powder and 18ml 10mol/L NaOH solution mix and add reactor and stir, after half hour, place baking oven to be heated to 110 ℃ autoclave, insulation 20h.
3. the autoclave that will react takes out, treat naturally cooling after, centrifugal, outwell supernatant liquid, precipitate with deionized water is washed until neutrality, use 0.1mol/L salt acid soak half hour again, with deionized water product is washed neutrality once more afterwards.
4. products therefrom is tiled in the watch-glass, put into baking oven with 100 ℃ of baking 12h, the block that takes out after drying grinds gently.Product after grinding is put into retort furnace with 400 ℃ of sintering temperature 2.5h, and then after grinding gently once more, promptly make required TiO
2Nanotube.
Claims (4)
1, a kind of method of utilizing pre-synthesis method of two steps to prepare doped titanic oxide nano tube.It is characterized in that preparing earlier adulterated titania nanoparticles, adulterated titania nanoparticles is mixed with highly basic carry out hydro-thermal reaction then,, obtain doped titanic oxide nano tube after the calcining through washing.
2, the method for the adulterated titania nanoparticles of preparation according to claim 1 it is characterized in that making impurity element enter the titanium dioxide lattice or with the titanium dioxide lattice in atom form chemical bond.The preparation method can be sol-gel method, hydrolysis method, coprecipitation method or scorification.
3, the feature of the doped element in the adulterated titania nanoparticles of preparation according to claim 1 is close with titanium or oxonium ion radius, can mix the titanium dioxide lattice, can be: B, N, P, S, C, F, Cl, Sn, Fe, In, Ni, W, Zn, Au, Pt.
4, adulterated titania nanoparticles according to claim 1 mixes hydro-thermal reaction and the washing of carrying out with highly basic, and calcination process is:
A) with 0.4g doped Ti O
2Nanometer powder and 18ml 10mol/L NaOH solution mix and add reactor and stir, after half hour, place baking oven to be heated to 110 ℃ autoclave, insulation 20h.
The autoclave that b) will react takes out, treat naturally cooling after, centrifugal, outwell supernatant liquid, precipitate with deionized water is washed until neutrality, use 0.1mol/L salt acid soak half hour again, with deionized water product is washed neutrality once more afterwards.
C) with grinding gently after the products therefrom oven dry, with 400 ℃ of sintering temperature 2.5h, promptly make required TiO then
2Nanotube.
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| CNA2008100537374A CN101302036A (en) | 2008-07-03 | 2008-07-03 | Preparation of doped titanium dioxide nano-tube |
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|---|---|---|---|
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Cited By (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| MD4063C1 (en) * | 2010-02-18 | 2011-03-31 | Технический университет Молдовы | Method for producing nanotubes of titanium dioxide on a titanium substrate |
| CN102157732A (en) * | 2011-03-24 | 2011-08-17 | 河南大学 | Titanium dioxide/carbon composite nanotube and preparation and application thereof |
| CN102863046A (en) * | 2012-09-09 | 2013-01-09 | 桂林理工大学 | Application of Au/TiO2 nanotube array in photocatalytic degradation of sugar wastewater |
| WO2013139174A1 (en) * | 2012-03-19 | 2013-09-26 | The Hong Kong University Of Science And Technology | Incorporating metals, metal oxides and compounds on the inner and outer surfaces of nanotubes and between the walls of the nanotubes and preparation thereof |
| CN103531762A (en) * | 2013-10-23 | 2014-01-22 | 山东大学 | Preparation method of titanium dioxide nano tube doped with heterovalent metal salt |
| CN104084205A (en) * | 2014-07-24 | 2014-10-08 | 哈尔滨工业大学 | Preparation method and application of ferrum loaded titanium dioxide nanotube with catalytic oxidation activity |
| CN104722294A (en) * | 2015-02-15 | 2015-06-24 | 福建工程学院 | Preparation technology of Pt-TiO2 nano-tube under normal pressure |
| CN105271388A (en) * | 2015-10-10 | 2016-01-27 | 同济大学 | Preparation method of high specific surface area ultralong TiO2 nanotube |
| CN105800680A (en) * | 2016-03-14 | 2016-07-27 | 武汉理工大学 | Preparation method of titanium dioxide nanotube doped with transition metal |
| CN108187651A (en) * | 2017-12-28 | 2018-06-22 | 山东纳安环保科技有限公司 | A kind of preparation method and application for carrying zinc nano-titanium dioxide |
| CN108465461A (en) * | 2018-03-26 | 2018-08-31 | 江苏奥净嘉环保科技有限公司 | A kind of preparation method of photocatalysis air-cleaning material |
| CN111364051A (en) * | 2020-03-23 | 2020-07-03 | 江苏大学 | Method for doping In ions to titanium dioxide photoelectrode by flame |
| CN112742414A (en) * | 2019-10-29 | 2021-05-04 | 中国石油化工股份有限公司 | Water-resistant and sulfur-resistant low-temperature SCR denitration catalyst and preparation method and application thereof |
| CN113368865A (en) * | 2021-06-08 | 2021-09-10 | 中国科学院山西煤炭化学研究所 | Denitration catalyst, preparation method thereof and waste gas denitration method |
| CN116159559A (en) * | 2022-12-16 | 2023-05-26 | 中国科学院福建物质结构研究所 | Preparation method and application of ruthenium-doped titanium dioxide nanotube catalyst |
-
2008
- 2008-07-03 CN CNA2008100537374A patent/CN101302036A/en active Pending
Cited By (21)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| MD4063C1 (en) * | 2010-02-18 | 2011-03-31 | Технический университет Молдовы | Method for producing nanotubes of titanium dioxide on a titanium substrate |
| CN102157732A (en) * | 2011-03-24 | 2011-08-17 | 河南大学 | Titanium dioxide/carbon composite nanotube and preparation and application thereof |
| US10238762B2 (en) | 2012-03-19 | 2019-03-26 | The Hong Kong University Of Science And Technology | Incorporating metals, metal oxides and compounds on the inner and outer surfaces of nanotubes and between the walls of the nanotubes and preparation thereof |
| WO2013139174A1 (en) * | 2012-03-19 | 2013-09-26 | The Hong Kong University Of Science And Technology | Incorporating metals, metal oxides and compounds on the inner and outer surfaces of nanotubes and between the walls of the nanotubes and preparation thereof |
| CN104350011A (en) * | 2012-03-19 | 2015-02-11 | 香港科技大学 | Incorporating metals, metal oxides and compounds on the inner and outer surfaces of nanotubes and between the walls of the nanotubes and preparation thereof |
| CN104350011B (en) * | 2012-03-19 | 2016-09-28 | 香港科技大学 | Doping metals, metal-oxide and metal complex and the preparation method of nanotube between the inner surface of nanotube and outer surface and nanotube layer |
| CN102863046A (en) * | 2012-09-09 | 2013-01-09 | 桂林理工大学 | Application of Au/TiO2 nanotube array in photocatalytic degradation of sugar wastewater |
| CN103531762A (en) * | 2013-10-23 | 2014-01-22 | 山东大学 | Preparation method of titanium dioxide nano tube doped with heterovalent metal salt |
| CN103531762B (en) * | 2013-10-23 | 2015-08-26 | 山东大学 | A kind of preparation method of titania nanotube of aliovalent slaine doping |
| CN104084205A (en) * | 2014-07-24 | 2014-10-08 | 哈尔滨工业大学 | Preparation method and application of ferrum loaded titanium dioxide nanotube with catalytic oxidation activity |
| CN104722294A (en) * | 2015-02-15 | 2015-06-24 | 福建工程学院 | Preparation technology of Pt-TiO2 nano-tube under normal pressure |
| CN105271388A (en) * | 2015-10-10 | 2016-01-27 | 同济大学 | Preparation method of high specific surface area ultralong TiO2 nanotube |
| CN105800680A (en) * | 2016-03-14 | 2016-07-27 | 武汉理工大学 | Preparation method of titanium dioxide nanotube doped with transition metal |
| CN108187651A (en) * | 2017-12-28 | 2018-06-22 | 山东纳安环保科技有限公司 | A kind of preparation method and application for carrying zinc nano-titanium dioxide |
| CN108465461A (en) * | 2018-03-26 | 2018-08-31 | 江苏奥净嘉环保科技有限公司 | A kind of preparation method of photocatalysis air-cleaning material |
| CN112742414A (en) * | 2019-10-29 | 2021-05-04 | 中国石油化工股份有限公司 | Water-resistant and sulfur-resistant low-temperature SCR denitration catalyst and preparation method and application thereof |
| CN112742414B (en) * | 2019-10-29 | 2022-10-21 | 中国石油化工股份有限公司 | Water-resistant and sulfur-resistant low-temperature SCR denitration catalyst and preparation method and application thereof |
| CN111364051A (en) * | 2020-03-23 | 2020-07-03 | 江苏大学 | Method for doping In ions to titanium dioxide photoelectrode by flame |
| CN113368865A (en) * | 2021-06-08 | 2021-09-10 | 中国科学院山西煤炭化学研究所 | Denitration catalyst, preparation method thereof and waste gas denitration method |
| CN113368865B (en) * | 2021-06-08 | 2022-12-02 | 中国科学院山西煤炭化学研究所 | Denitration catalyst, preparation method thereof and waste gas denitration method |
| CN116159559A (en) * | 2022-12-16 | 2023-05-26 | 中国科学院福建物质结构研究所 | Preparation method and application of ruthenium-doped titanium dioxide nanotube catalyst |
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Open date: 20081112 |