CN1307328C - Preparation method of one-dimensional single crystal titanium dioxide nano material - Google Patents
Preparation method of one-dimensional single crystal titanium dioxide nano material Download PDFInfo
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- CN1307328C CN1307328C CNB2004100380736A CN200410038073A CN1307328C CN 1307328 C CN1307328 C CN 1307328C CN B2004100380736 A CNB2004100380736 A CN B2004100380736A CN 200410038073 A CN200410038073 A CN 200410038073A CN 1307328 C CN1307328 C CN 1307328C
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Abstract
本发明属于纳米材料技术领域，(1)将1～30份四氯化钛或二氧化钛粉体加入到70～99份有机溶剂中，得到分散均匀的混合物；(2)将10～60份氢氧化钠溶于40～90份去离子水中，得到氢氧化钠水溶液；(3)往10～50份步骤(1)的混合物中加入20～80份步骤(2)的氢氧化钠水溶液，搅拌，转移到高压釜中，在50～300℃温度下恒温；(4)冷却，倾去上层清液，用去离子水和酸的稀溶液洗涤、离心、收集下层沉淀，在10～200℃干燥，得到长度在微米数量级，直径在10～100nm的一维单晶二氧化钛纳米材料(纳米线、纳米棒、纳米管)。产品纯度、产率高，可以通过选择不同的溶剂实现形态和形貌的调控。The invention belongs to the technical field of nanomaterials. (1) adding 1 to 30 parts of titanium tetrachloride or titanium dioxide powder into 70 to 99 parts of an organic solvent to obtain a uniformly dispersed mixture; (2) oxidizing 10 to 60 parts of hydrogen Dissolve sodium in 40-90 parts of deionized water to obtain aqueous sodium hydroxide solution; (3) add 20-80 parts of aqueous sodium hydroxide solution in step (2) to 10-50 parts of the mixture in step (1), stir, and transfer (4) cooling, pouring off the supernatant, washing with dilute solution of deionized water and acid, centrifuging, collecting the lower precipitate, and drying at 10-200°C to obtain One-dimensional single crystal titanium dioxide nanomaterials (nanowires, nanorods, nanotubes) with a length on the order of microns and a diameter of 10 to 100 nm. The product has high purity and high yield, and the morphology and morphology can be adjusted by selecting different solvents.
Description
Technical field
The invention belongs to technical field of nano material, relate generally to the preparation method of one-dimensional single crystal titanium dioxide nano material (nano wire, nanometer rod, nanotube).
Background technology
Monodimension nanometer material has wide practical use in fields such as optics, electronics, environment and medical science, becomes the focus of material area research.Titanium dioxide is as a kind of n N-type semiconductorN and a kind of typical photocatalyst, in the broad prospect of application of aspects such as opto-electronic conversion, photovoltaic device, photocatalytic degradation pollutent and photodissociation water generates hydrogen and attracted attention by the people.At present, carrying out certain research work aspect the preparation of one-dimensional single crystal titanium dioxide nano material, preparation method commonly used mainly contains two kinds, and a kind of is template, and a kind of is hydrothermal method.The report of this respect can be referring to " chemical material " 2002 the 14th volumes the 1391st page of (Liu, S.M.; Gan, L.M.; Liu, L.H.; Zhang, W.D.; Zeng, H.C.Chem.Mater., 2002,14,1391.), calendar year 2001 the 13rd volume the 2511st page of (Zhang, X.Y.; Zhang, L.D.; Chen, W.; Meng, G.W.; Zheng, M.J.; Zhao, L.X.Chem.Mater., 2001,13,2511.) and " chemical physics wall bulletin " 2002 the 365th volumes the 300th page of (Zhang, Y.X.; Li, G.H.; Jin, Y.X.; Zhang, Y.; Zhang, J.; Zhang, L.D.Chem.Phys.Lett.2002,365,300.) etc.Before a kind of method be the utilization anodised aluminium as template, with the alkoxide of the halogenide of titanium and titanium as precursor, by sol-gel method growth titania nanotube and nano wire; The back a kind of method be the utilization hydrothermal method with the anatase titanium dioxide powder as precursor, by solution chemistry method growth titanium dioxide nano thread.Though preceding a kind of method has obtained highly purified single crystal titanium dioxide nanowire and nanotube, the experiment flow complexity; A kind of method experiment flow in back is simple relatively, but the titanium dioxide nano thread purity of preparation is not enough, a considerable amount of brookites have been mingled with in the anatase octahedrite, moreover, the raw material that preceding a kind of method is used is generally the higher metal alkoxide of price, cost is higher, and the titanium dioxide nano thread and the nanotube aspect ratio of preparation are not high.Two kinds of methods of what is more important are the control of the regulation and control of condition and experiment parameter realization form and pattern by experiment all.
Summary of the invention
One of purpose of the present invention provides a kind of a large amount of method for preparing one-dimensional single crystal titanium dioxide nano material (nano wire, nanometer rod, nanotube).
Another object of the present invention is that metal inorganic salt and metal oxide cheap more with relative metal alkoxide, that be easy to get are main raw material (as titanium tetrachloride, titanium dioxide powder), the utilization solvent-thermal method prepares one-dimensional single crystal titanium dioxide nano material (nano wire, nanometer rod, nanotube), realizes the control of product form and pattern by selecting different solvents.
The objective of the invention is to realize by following technical proposals:
(1) solvent-thermal method prepares one-dimensional single crystal titanium dioxide nano material (nano wire, nanometer rod, nanotube).
(2) select different solvents, the form and the pattern of regulation and control product.
The preparation of one-dimensional single crystal titanium dioxide nano material among the present invention is to be raw material with titanium tetrachloride or titanium dioxide powder, the preparation of utilization solvent-thermal method.This method may further comprise the steps, and related amount is in parts by weight:
(1) 1～30 part of titanium tetrachloride or titanium dioxide powder are joined in the organic solvent of 70～99 parts of alcohol, amine, nitrile or phenols, vigorous stirring obtains the mixture of the organic solvent of finely dispersed titanium tetrachloride or titanium dioxide;
(2) 10～60 parts of sodium hydroxide are dissolved in 40～90 parts of deionized waters, stir, obtain transparent, clarifying aqueous sodium hydroxide solution;
(3) under stirring fast, add the aqueous sodium hydroxide solution of 20～80 parts of steps (2) in the mixture of 10～50 parts of steps (1), after the lasting stirred for several minute, transfer in the teflon-lined autoclave constant temperature under 50～300 ℃ of temperature;
(4) naturally cooling, the supernatant liquid that inclines, (concentration 10～200 ℃ of dryings, obtains the one-dimensional single crystal titanium dioxide nano material in 0～1.0M) washing, centrifugal, collection lower sediment with sour dilute solution with deionized water.
Described step (3) constant temperature time is 0.5～72 hour.
Described nitrile is fatty nitrile or fragrant nitrile, as acetonitrile or o-methyl-benzene nitrile etc.
Described phenol is monohydric phenol or polyphenol, as phenol, Resorcinol or Phloroglucinol etc.
Described alcohol is monohydroxy-alcohol, dibasic alcohol or polyvalent alcohol.Described monohydroxy-alcohol is methyl alcohol, ethanol or butanols etc.; Dibasic alcohol is ethylene glycol or 2,5-heptanediol etc.; Described polyvalent alcohol is a glycerol etc.
Described amine is aliphatic amide or aromatic amine etc.Described aliphatic amide is amino dodecane, quadrol or diethanolamine etc.; Described aromatic amine is an aniline etc.
Described acid is mineral acids such as hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, or organic acid such as acetate, citric acid, tartrate.
The length of described one-dimensional single crystal titanium dioxide nano material (nano wire, nanometer rod, nanotube) is in the micron number magnitude.
The one-dimensional single crystal titanium dioxide nano material (nano wire, nanometer rod, nanotube) of the inventive method preparation has been realized the regulation and control of different shape and pattern by choice of Solvent.
Advantage of the present invention and positively effect:
The one-dimensional single crystal titanium dioxide nano material that method of the present invention is prepared (nano wire, nanometer rod, nanotube) is compared with general method, has the following advantages:
1. raw materials used low price, be easy to get:
When adopting the one-dimensional single crystal titanium dioxide nano material (nano wire, nanometer rod, nanotube) of method preparation of the present invention, with titanium tetrachloride or titanium dioxide powder is main raw material(s), used starting material are that raw material is cheaply a lot of with the metal alkoxide with template, and raw material is easy to get.
2. product purity is very high, does not almost have other impurity:
Adopt the one-dimensional titanium dioxide nano material (nano wire, nanometer rod, nanotube) of the present invention's preparation, have single crystal structure, do not have impurity peaks, as shown in Figure 1.
3. product productive rate height can be realized scale operation.
The one-dimensional single crystal titanium dioxide nano material (nano wire, nanometer rod, nanotube) that adopts method of the present invention to prepare, productive rate almost can reach 100%, does not observe by product in the experiment, as shown in Figure 2.
4. Zhi Bei one-dimensional titanium dioxide nano material (nano wire, nanometer rod, nanotube) has perfect single crystal structure:
At present, the one-dimensional titanium dioxide nano material of method preparation commonly used is amorphous and polycrystalline mostly, and monocrystalline is difficult to obtain, and defective is more, adopts the one-dimensional single crystal titanium dioxide nano material of the present invention's preparation that perfect single crystal structure is arranged, as shown in Figure 3.
5. the preparation method is simple, easily row:
Method of the present invention is when preparation one-dimensional single crystal titanium dioxide nano material (nano wire, nanometer rod, nanotube), and method is simple, easy goes.
6. compare with general method, the one-dimensional single crystal titanium dioxide nano material that method of the present invention is prepared (nano wire, nanometer rod, nanotube) has very high aspect ratio, and length is in the micron number magnitude, and diameter is at 10～100nm.
Description of drawings
Fig. 1. the XRD figure of the one-dimensional single crystal titanium dioxide nano thread of the embodiment of the invention 3 preparations.
Fig. 2. the tunnel stereoscan photograph of the one-dimensional single crystal titanium dioxide nano thread of the embodiment of the invention 8 preparations.
Fig. 3. the tunnel stereoscan photograph of the one-dimensional single crystal titanium dioxide nano thread of the embodiment of the invention 3 preparations.
Fig. 4. the high-resolution-ration transmission electric-lens photo of the one-dimensional single crystal titanium dioxide nano thread of the embodiment of the invention 3 preparations.
Embodiment
Embodiment 1
Get the commercial P25 powder of 25 weight parts and join in the 75 weight part butanols, vigorous stirring obtains finely dispersed mixture; Under stirring fast, the 50 weight part sodium hydroxide that add 70 weight parts in 30 weight part said mixtures are dissolved in the solution that is generated in the deionized water of 50 weight parts, after continuing stirred for several minute, be transferred in the teflon-lined autoclave, 110 ℃ of constant temperature 8 hours naturally cools to room temperature.The supernatant liquid that inclines, deionized water and dilute sulphuric acid washing lower sediment are for several times, and be centrifugal, and 60 ℃ of dryings are 12 hours in baking oven, obtain the one-dimensional single crystal titanium dioxide nano thread.
Embodiment 2
Get 1 weight part anatase titanium dioxide powder and add in the 99 weight part amino dodecanes, vigorous stirring obtains finely dispersed mixture; Under stirring fast, the 15 weight part sodium hydroxide that add 82 weight parts in 18 weight part said mixtures are dissolved in the solution that is generated in the deionized water of 85 weight parts, after continuing stirred for several minute, be transferred in the teflon-lined autoclave, 150 ℃ of constant temperature 2 hours naturally cools to room temperature.The supernatant liquid that inclines, deionized water and acetic acid,diluted washing lower sediment are for several times, and be centrifugal, and 120 ℃ of dryings are two days in baking oven, obtain the one-dimensional single crystal titanium dioxide nano-rod.
Embodiment 3
Get the commercial P25 powder of 15 weight parts and add in 85 parts by weight of ethanol, vigorous stirring obtains finely dispersed mixture; Under stirring fast, the 25 weight part sodium hydroxide that add 50 weight parts in 50 weight part said mixtures are dissolved in the solution that is generated in the deionized water of 75 weight parts, after continuing stirred for several minute, be transferred in the teflon-lined autoclave, 200 ℃ of constant temperature 16 hours naturally cools to room temperature.The supernatant liquid that inclines, deionized water and rare nitric acid washing lower sediment are for several times, and be centrifugal, at room temperature dry three days, obtains the one-dimensional single crystal titanium dioxide nano thread.
Embodiment 4
Get 6 weight part titanium tetrachlorides and add in the 94 weight part ethylene glycol, vigorous stirring obtains finely dispersed mixture; Under stirring fast, the 35 weight part sodium hydroxide that add 80 weight parts in 20 weight part said mixtures are dissolved in the solution that is generated in the deionized water of 65 weight parts, after continuing stirred for several minute, be transferred in the teflon-lined autoclave, 240 ℃ of constant temperature 48 hours naturally cools to room temperature.The supernatant liquid that inclines, deionized water and dilute hydrochloric acid washing lower sediment are for several times, and be centrifugal, and 100 ℃ of dryings are 6 hours in baking oven, obtain the one-dimensional single crystal titanium dioxide nano thread, and length is at several micron～hundreds of microns, and diameter is at 20～50nm.
Embodiment 5
Get 25 weight part rutile titanium dioxide powders and add in the 75 weight part glycerol, vigorous stirring obtains finely dispersed mixture; Under stirring fast, the 10 weight part sodium hydroxide that add 55 weight parts in 45 weight part said mixtures are dissolved in the solution that is generated in the deionized water of 90 weight parts, after continuing vigorous stirring number minute, be transferred in the teflon-lined autoclave, 180 ℃ of constant temperature 2 hours naturally cools to room temperature.The supernatant liquid that inclines, deionized water and rare citric acid washing lower sediment are for several times, and be centrifugal, and 200 ℃ of dryings are 8 hours in baking oven, obtain the one-dimensional single crystal titania nanotube.
Embodiment 6
Get the commercial P25 powder of 30 weight parts and add in the 70 weight part acetonitriles, vigorous stirring obtains finely dispersed mixture; Under stirring fast, the 20 weight part sodium hydroxide that add 75 weight parts in 25 weight part said mixtures are dissolved in the solution that is generated in the deionized water of 80 weight parts, after continuing stirred for several minute, be transferred in the teflon-lined autoclave, 80 ℃ of constant temperature 12 hours naturally cools to room temperature.The supernatant liquid that inclines, deionized water and dilute hydrochloric acid washing lower sediment are for several times, and be centrifugal, and 80 ℃ of dryings are 4 hours in baking oven, obtain the one-dimensional single crystal titanium dioxide nano-rod.
Embodiment 7
Get 10 weight part anatase titanium dioxide powders and add in the 90 weight part quadrols, vigorous stirring obtains finely dispersed mixture; Under stirring fast, the 40 weight part sodium hydroxide that add 85 weight parts in 15 weight part said mixtures are dissolved in the solution that is generated in the deionized water of 60 weight parts, continuously and healthily after the stirred for several minute, be transferred in the teflon-lined autoclave, 300 ℃ of constant temperature 24 hours naturally cools to room temperature.The supernatant liquid that inclines, deionized water and rare nitric acid washing lower sediment are for several times, and be centrifugal, at room temperature dry a couple of days, obtains the one-dimensional single crystal titania nanotube, and length is hundreds of microns, and diameter is at 80～100nm.
Embodiment 8
Get the commercial P25 powder of 20 weight parts and add in the 80 weight part phenol, vigorous stirring obtains finely dispersed mixture; Under stirring fast, the 40 weight part sodium hydroxide that add 64 weight parts in 36 weight part said mixtures are dissolved in the solution that is generated in the deionized water of 60 weight parts, after continuing vigorous stirring number minute, be transferred in the teflon-lined autoclave, 200 ℃ of constant temperature 72 hours naturally cools to room temperature.The supernatant liquid that inclines, deionized water and dilute acetic acid washing lower sediment are for several times, and be centrifugal, and 80 ℃ of dryings are 6 hours in baking oven, obtain the one-dimensional single crystal titanium dioxide nano thread.
Claims (10)
1. the preparation method of an one-dimensional single crystal titanium dioxide nano material, it is characterized in that: this method may further comprise the steps, and related amount is in parts by weight:
(1) 1～30 part of titanium tetrachloride or titanium dioxide powder are joined in the organic solvent of 70～99 parts of alcohol, amine, nitrile or phenols, vigorous stirring obtains the mixture of the organic solvent of finely dispersed titanium tetrachloride or titanium dioxide;
(2) 10～60 parts of sodium hydroxide are dissolved in 40～90 parts of deionized waters, stir, obtain aqueous sodium hydroxide solution;
(3) stir down, add the aqueous sodium hydroxide solution of 20～80 parts of steps (2) in the mixture of 10～50 parts of steps (1), after the lasting vigorous stirring, transfer in the autoclave constant temperature under 50～300 ℃ of temperature;
(4) cool off, the supernatant liquid that inclines with the dilute solution washing of deionized water and acid, centrifugal, collection lower sediment, 10～200 ℃ of dryings, obtains the one-dimensional single crystal titanium dioxide nano material.
2. method according to claim 1 is characterized in that: described step (3) constant temperature time is 0.5～72 hour.
3. method according to claim 1 is characterized in that: described nitrile is acetonitrile or o-methyl-benzene nitrile.
4. method according to claim 1 is characterized in that: described phenol is phenol, Resorcinol or Phloroglucinol.
5. method according to claim 1 is characterized in that: described alcohol is monohydroxy-alcohol, dibasic alcohol or polyvalent alcohol.
6. method according to claim 5 is characterized in that: described monohydroxy-alcohol is methyl alcohol, ethanol or butanols; Described dibasic alcohol is ethylene glycol or 2, the 5-heptanediol; Described polyvalent alcohol is a glycerol.
7. method according to claim 1 is characterized in that: described amine is aliphatic amide or aromatic amine.
8. method according to claim 7 is characterized in that: described aliphatic amide is amino dodecane, quadrol or diethanolamine; Described aromatic amine is an aniline.
9. method according to claim 1 is characterized in that: described acid is hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, acetate, citric acid or tartrate.
10. method according to claim 1 is characterized in that: the form of described one-dimensional single crystal titanium dioxide nano material comprises nano wire, nanometer rod or nanotube, and length is in the micron number magnitude, and diameter is at 10～100nm.
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Families Citing this family (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100441751C (en) * | 2005-12-20 | 2008-12-10 | 中国科学院兰州化学物理研究所 | Preparation method of oil-soluble titanium dioxide nanorods |
| KR100812357B1 (en) * | 2005-12-23 | 2008-03-11 | 한국과학기술연구원 | Ultra-sensitive metal oxide gas sensor and fbrication method thereof |
| 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 |
| WO2009101640A1 (en) * | 2008-02-11 | 2009-08-20 | Daunia Wind Srl | Process for the preparation of titanium dioxide with nanometric dimensions and controlled shape |
| CN101550595B (en) * | 2009-04-03 | 2011-07-20 | 哈尔滨工业大学 | Method for preparing pure rutile-phase titanium dioxide single crystalline nanorod without template under low temperature |
| CN101845664B (en) * | 2010-06-18 | 2011-11-16 | 西安交通大学 | Low-temperature preparation method of highly oriented single crystal titanium dioxide nanowire array film |
| CN101920990A (en) * | 2010-07-23 | 2010-12-22 | 上海师范大学 | A method for preparing titanium dioxide nanowires by high-pressure microwave method |
| CN101994154B (en) * | 2010-11-26 | 2012-06-06 | 浙江大学 | Preparation method of waist drum shaped single crystal anatase titanium dioxide and gathered microsphere thereof |
| CN102241414B (en) * | 2011-05-25 | 2013-11-13 | 东华大学 | Method for preparing hydrophilic-lypophilic controllable anatase titanium dioxide nanoparticles |
| CN102897831B (en) * | 2012-10-30 | 2015-01-07 | 东华大学 | Method for preparing oil-soluble anatase type nanometer titanium dioxide particles by using oil-water interface method |
| CN103553127B (en) * | 2013-10-22 | 2015-11-25 | 渤海大学 | The preparation method of anatase type titanium dioxide nano tube |
| CN110947410B (en) * | 2019-12-11 | 2023-10-24 | 信阳师范学院 | A gentle preparation method for nitrogen-doped TiO2 micron beams |
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| CN1400169A (en) * | 2002-08-19 | 2003-03-05 | 西安华创纳米化合物技术研究发展有限责任公司 | Preparation method of titanium oxide nano fibre |
| CN1440930A (en) * | 2002-02-26 | 2003-09-10 | 舟山明日纳米材料有限公司 | Prepn process of nano rutile-type titania |
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| CN1440930A (en) * | 2002-02-26 | 2003-09-10 | 舟山明日纳米材料有限公司 | Prepn process of nano rutile-type titania |
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