CN103274458A - One-dimensional necklace-shaped titanium dioxide nanocrystal and preparation method thereof - Google Patents
One-dimensional necklace-shaped titanium dioxide nanocrystal and preparation method thereof Download PDFInfo
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- CN103274458A CN103274458A CN2013102199693A CN201310219969A CN103274458A CN 103274458 A CN103274458 A CN 103274458A CN 2013102199693 A CN2013102199693 A CN 2013102199693A CN 201310219969 A CN201310219969 A CN 201310219969A CN 103274458 A CN103274458 A CN 103274458A
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Abstract
The invention discloses a one-dimensional necklace-shaped titanium dioxide nanocrystal and a preparation method thereof. The crystal structure of the nanocrystal is an anatase type. The nanocrystal is formed through orientation contact among basic units, and the basic units are tetragonal dipyramids with vertex angles being cut. The growth directions of the nanocrystal is [001] crystal direction. The length range of the nanocrystal is from 15 to 400nm. The preparation method comprises the following steps: adding a titanium source precursor into an organic solvent, stirring the mixture evenly, then adding sodium fluoride, and stirring at room temperature; transferring the mixed solution into a stainless steel reactor, closing the reactor and maintaining the reactor at 150-200 DEG C for 12-36 hours, and then naturally cooling; adding a hydroxyl donor, stirring at the room temperature; transferring the obtained solution into the stainless steel reactor, closing the reactor and maintaining the reactor at 250-300 DEG C for 12-36 hours, and then naturally cooling; washing the reaction product by filtering, drying, grinding, and finally obtaining the target product. The one-dimensional nanocrystal of the invention has good crystallization and a controllable length in the [001] direction. Compared with other one-dimensional nanowires, the one-dimensional nanocrystal has a higher specific surface area.
Description
Technical field
The present invention relates to a kind of titanium dioxide nano material, especially a kind of have one dimension item chain titanium dioxide nano-crystal and preparation method thereof, belongs to the preparation field of chemical material, in the clean energy field very important purposes arranged.
Background technology
Environmental pollution and energy dilemma are two sixty-four dollar questions running in the present human social development; degraded to environmental pollutants and to being that the exploitation of the new forms of energy of representative has caused the great attention of countries in the world governments with sun power also is the focus of present scientist's research.Detitanium-ore-type TiO
2Have hypotoxicity, advantage such as chemical stability is good, and is corrosion-resistant, and can utilize the photon degradable organic pollutant of certain wavelength, therefore be considered to a kind of important environment protection material.
Simultaneously, TiO
2Be a kind of light anode material commonly used in dye sensitization solar battery, generally the nano particle as the light anode material is particulate state, has a large amount of crystal boundaries between the particle, so electronics has very big loss owing to the crystal boundary scattering in transmission course.The one-dimensional single crystal nano material has good electronic transmission performance, is used in to be considered to a kind of good light anode material in the dye sensitization solar battery.A large amount of theoretical investigation and experiments show that the nano material with one-dimensional single crystal structure has excellent performance aspect electric transmission, and electronics is not vulnerable to the scattering of crystal boundary when crystals transmits, thereby has improved the transmittability of electronics.At present, the synthetic and applied research to one dimension and accurate one-dimensional titanium dioxide nanocrystal has report.People (Nanorod Based Dye Sensitized Solar Cells with Improved Charge Collection Efficiency. Adv. Mater. 2008. 20 such as Soon Hyung Kang, 54 ~ 58) titanium dioxide nano-rod that will synthesize is applied to the light anode of dye sensitization solar battery, has improved electron transport ability.But the forming process of the nanometer rod of using in this research is based on Ostwald ripening, plane of crystal is smooth, and specific surface area is less, so when being used as the light anode, reduced the adsorptive capacity of dyestuff, this also is the general deficiency of the monodimension nanometer material that obtains by Ostwald ripening at present.People such as Penn (Morphology development and crystal growth in nanocrystalline aggregates under hydrothermal conditions:Insights from titania. Geochim. Cosmochim. Acta 1999,63,1549 ~ 1557) find that the earliest titanium dioxide nano-crystal can the orientation contact take place at (001) crystal face, namely intergranule forms bigger crystal grain by the fusion of crystal face.People (Shape Evolution of Highly Crystalline Anatase TiO2 Nanobipyramids. Cryst. Growth Des. 2011 such as Chen afterwards, 11,5221 ~ 5226.) find to have the exposed titania nanoparticles of (001) face the orientation contact more easily takes place.But these researchs can't separate Ostwald ripening process and orientation contact process effectively, and then the length of uncontrollable one-dimentional structure, and the crystal number of generation oriented growth is less, and the length of the nanostructure of acquisition is shorter.
Summary of the invention
In order to overcome the deficiencies in the prior art, the object of the present invention is to provide a kind of preparation to have the one dimension item chain TiO of high crystalline
2Preparation of nanomaterials.The present invention utilizes two step solvent-thermal methods effectively Ostwald ripening and orientation contact process to be separated, and by higher temperature in the second step solvent thermal process, trigger the generation of orientation contact on [001] direction, the one dimension item chain titanium dioxide that is synthesized has higher crystallinity, and length can change by regulating synthesis condition within the specific limits.
A kind of one dimension item chain titanium dioxide nano-crystal, its crystalline structure is Detitanium-ore-type, and elementary cell is a plurality of tetragonal bipyramid bodies of clipping drift angle, and the direction of growth is [001] crystal orientation, forms by the orientation contact, and length range is 15 ~ 400 nm.
A kind of preparation method of described one dimension item chain titanium dioxide nano-crystal comprises the steps:
1) the titanium source presoma of 1 ~ 10ml is joined in the organic solvent of 20 ~ 50ml and stir, and then add 0.01 ~ 1g Sodium Fluoride, at room temperature stirred again 6 ~ 24 hours, be mixed with mixing solutions;
2) mixing solutions that obtains in the step 1) is moved in the stainless steel cauldron, airtight back kept under 150 ~ 200 ℃ temperature 12 ~ 36 hours, naturally cooled to room temperature then;
3) toward step 2) add the hydroxyl donor of 0.1 ~ 5ml in the solution that obtains, stirred under the room temperature 6 ~ 24 hours;
4) solution that step 3) is obtained moves in the stainless steel cauldron, and airtight back kept under 250 ~ 300 ℃ temperature 12 ~ 36 hours, was cooled to room temperature then;
5) reaction product of utilizing acetone, alcohol diafiltration step 4) to obtain, oven dry is ground, and finally obtains target product.
Described target product is assembled by a plurality of tetragonal bipyramid bodies of clipping drift angle with the one-dimensional chain nanocrystal, and [001] direction is its preferential growth direction.
Described organic solvent is oleic acid or oleyl amine.
The described titanium of step 1) source presoma is one or more in the following titanium source: tetrabutyl titanate or metatitanic acid isopropyl alcohol ester.
The described hydroxyl donor of step 3) is one or more in the following reagent: water, ethanol, propyl alcohol.
With existing TiO
2The preparation of nano material is compared, and the present invention has the following advantages:
1. the 1-dimention nano crystal structure is good;
2. 1-dimention nano crystal length controlled on [001] direction;
3. compare with other one-dimensional nano lines, have higher specific surface area.
Description of drawings
The XRD spectra of the one-dimensional chain titanium dioxide nano-crystal of Fig. 1 the inventive method embodiment 1 preparation.
The transmission electron microscope photo of the one-dimensional chain titanium dioxide nano-crystal of Fig. 2 the inventive method embodiment 1 preparation.
The high-resolution-ration transmission electric-lens photo of the one-dimensional chain titanium dioxide nano-crystal of Fig. 3 the inventive method embodiment 1 preparation.
The transmission electron microscope photo of the one-dimensional chain titanium dioxide nano-crystal of Fig. 4 the inventive method embodiment 2 preparations.
Fig. 5 the inventive method example is executed the transmission electron microscope photo of the one-dimensional chain titanium dioxide nano-crystal of 3 preparations.
Embodiment
Following examples will be further described content of the present invention by reference to the accompanying drawings.These embodiment are interpreted as only being used for explanation the present invention and are not used in restriction protection scope of the present invention.After the content of having read the present invention's record, those skilled in the art can make various changes or modifications the present invention, and these equivalences change and modify and fall into claim of the present invention institute restricted portion equally.
A kind of one dimension item chain titanium dioxide nano-crystal, its crystalline structure is Detitanium-ore-type, form by the orientation contact that takes place between the elementary cell, elementary cell is a plurality of tetragonal bipyramid bodies of clipping drift angle, the direction of growth is [001] crystal orientation, form by the orientation contact, length range is 15 ~ 400 nm.
Embodiment 1
1) stirs in the oleic acid with the tetrabutyl titanate of 4 ml and 38ml, add the 0.5g Sodium Fluoride again, stirred 6 hours under the room temperature, be mixed with mixing solutions.
2) mixing solutions in the step 1) is moved in the stainless steel cauldron, airtight back kept 24 hours under 200 ℃ temperature, was cooled to room temperature then.
3) toward step 2) add 1.5 ml deionized waters in the solution that obtains, stirred 6 hours under the room temperature;
4) solution in the step 3) is moved in the stainless steel cauldron again, airtight back kept 24 hours under 300 ℃ temperature, was cooled to room temperature then.
5) utilize the filtration wash products of acetone, alcohol, oven dry is ground, and finally obtains target product.
Fig. 1 is the X ray diffracting spectrum of this target product, and as can be seen, product is Detitanium-ore-type, does not have dephasign, and the peak is narrow, peak shape is sharp-pointed and intensity is high, shows that crystalline structure is complete.Fig. 2 is the transmission electron microscope photo of this target product, and as can be seen, product mostly is one dimension item chain structure greatly, and most of product is arranged by 20 and above monomer and formed.Fig. 3 is the high-resolution-ration transmission electric-lens photo of this target product, and as can be seen, the product crystalline structure is complete, and the form with crystallization between the monomer connects, and monomer is shaped as the tetragonal bipyramid body of clipping drift angle.
Embodiment 2
1) stirs in the oleic acid with the tetrabutyl titanate of 4 ml and 38ml, add the 0.5g Sodium Fluoride again, stirred 6 hours under the room temperature, be mixed with mixing solutions.
2) mixing solutions in the step 1) is moved in the stainless steel cauldron, airtight back kept 24 hours under 200 ℃ temperature, was cooled to room temperature then.
3) toward step 2) add the 0.6ml deionized water in the solution that obtains, stirred 6 hours under the room temperature;
4) solution in the step 3) is moved in the stainless steel cauldron again, airtight back kept 24 hours under 300 ℃ temperature, was cooled to room temperature then.
5) utilize the filtration wash products of acetone, alcohol, oven dry is ground, and finally obtains target product.
Fig. 4 is the transmission electron microscope photo of this target product, and as can be seen, partial monosomy begins to take place the orientation contact in the product.
Embodiment 3
1) stirs in the oleic acid with the tetrabutyl titanate of 4 ml and 38ml, add the 0.5g Sodium Fluoride again, stirred 6 hours under the room temperature, be mixed with mixing solutions.
2) mixing solutions in the step 1) is moved in the stainless steel cauldron, airtight back kept 24 hours under 200 ℃ temperature, was cooled to room temperature then.
3) toward step 2) add the 0.6ml deionized water in the solution that obtains, stirred 6 hours under the room temperature;
4) solution in the step 3) is moved in the stainless steel cauldron again, airtight back kept 24 hours under 300 ℃ temperature, was cooled to room temperature then.
5) utilize the filtration wash products of acetone, alcohol, oven dry is ground, and finally obtains target product.
Fig. 5 is the transmission electron microscope photo of this target product, and as can be seen, most of product is one dimension item chain, and the monomer number is between 10 ~ 15.
1) stirs in the oleic acid with the tetrabutyl titanate of 1ml and 20ml, add the 0.01g Sodium Fluoride again, stirred 6 hours under the room temperature, be mixed with mixing solutions.
2) mixing solutions in the step 1) is moved in the stainless steel cauldron, airtight back kept 12 hours under 180 ℃ temperature, was cooled to room temperature then.
3) toward step 2) add 0.1 ml ethanol in the solution that obtains, stirred 6 hours under the room temperature;
4) solution in the step 3) is moved in the stainless steel cauldron again, airtight back kept 12 hours under 280 ℃ temperature, was cooled to room temperature then.
5) utilize the filtration wash products of acetone, alcohol, oven dry is ground, and finally obtains target product.
Embodiment 5
1) stirs in the oleic acid with the tetrabutyl titanate of 10ml and 50ml, add the 1g Sodium Fluoride again, stirred 24 hours under the room temperature, be mixed with mixing solutions.
2) mixing solutions in the step 1) is moved in the stainless steel cauldron, airtight back kept 36 hours under 150 ℃ temperature, was cooled to room temperature then.
3) toward step 2) add 5 ml deionized waters in the solution that obtains, stirred 24 hours under the room temperature;
4) solution in the step 3) is moved in the stainless steel cauldron again, airtight back kept 36 hours under 250 ℃ temperature, was cooled to room temperature then.
5) utilize the filtration wash products of acetone, alcohol, oven dry is ground, and finally obtains target product.
Embodiment 6
1) stirs in the oleyl amine with the tetrabutyl titanate of 4 ml and 38ml, add the 0.5g Sodium Fluoride again, stirred 6 hours under the room temperature, be mixed with mixing solutions.
2) mixing solutions in the step 1) is moved in the stainless steel cauldron, airtight back kept 24 hours under 200 ℃ temperature, was cooled to room temperature then.
3) toward step 2) add 1.2 ml propyl alcohol in the solution that obtains, stirred 6 hours under the room temperature;
4) solution in the step 3) is moved in the stainless steel cauldron again, airtight back kept 24 hours under 300 ℃ temperature, was cooled to room temperature then.
5) utilize the filtration wash products of acetone, alcohol, oven dry is ground, and finally obtains target product.
Claims (6)
1. one dimension item chain titanium dioxide nano-crystal, it is characterized in that, its crystalline structure is Detitanium-ore-type, form by the orientation contact that takes place between the elementary cell, elementary cell is a plurality of tetragonal bipyramid bodies of clipping drift angle, the direction of growth is [001] crystal orientation, and length range is 15 ~ 400 nm.
2. the preparation method of an one dimension item chain titanium dioxide nano-crystal according to claim 1 is characterized in that, comprises the steps:
1) the titanium source presoma of 1 ~ 10ml is joined in the organic solvent of 20 ~ 50ml and stir, and then add 0.01 ~ 1g Sodium Fluoride, at room temperature stirred again 6 ~ 24 hours, be mixed with mixing solutions;
2) mixing solutions that obtains in the step 1) is moved in the stainless steel cauldron, airtight back kept under 150 ~ 200 ℃ temperature 12 ~ 36 hours, naturally cooled to room temperature then;
3) toward step 2) add the hydroxyl donor of 0.1 ~ 5ml in the solution that obtains, stirred under the room temperature 6 ~ 24 hours;
4) solution that step 3) is obtained moves in the stainless steel cauldron, and airtight back kept under 250 ~ 300 ℃ temperature 12 ~ 36 hours, was cooled to room temperature then;
5) reaction product of utilizing acetone, alcohol diafiltration step 4) to obtain, oven dry is ground, and finally obtains target product.
3. preparation method according to claim 2 is characterized in that, described organic solvent is oleic acid or oleyl amine.
4. preparation method according to claim 2 is characterized in that, described target product is assembled by a plurality of tetragonal bipyramid bodies of clipping drift angle with the one-dimensional chain nanocrystal, and [001] direction is its preferential growth direction.
5. preparation method according to claim 2 is characterized in that, the described titanium of step 1) source presoma is one or more in the following titanium source: tetrabutyl titanate or metatitanic acid isopropyl alcohol ester.
6. preparation method according to claim 2 is characterized in that, the described hydroxyl donor of step 3) is one or more in the following reagent: water, ethanol, propyl alcohol.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108465478A (en) * | 2017-02-23 | 2018-08-31 | 中国石油化工股份有限公司 | Nanoassemble mordenite catalyst and preparation method thereof |
| CN108465480A (en) * | 2017-02-23 | 2018-08-31 | 中国石油化工股份有限公司 | Special appearance mordenite catalyst and preparation method thereof |
| CN108465479A (en) * | 2017-02-23 | 2018-08-31 | 中国石油化工股份有限公司 | Self assembly special appearance mordenite catalyst and preparation method thereof |
| CN108499595A (en) * | 2017-02-23 | 2018-09-07 | 中国石油化工股份有限公司 | Special appearance mordenite catalyst |
| CN111446330A (en) * | 2020-03-31 | 2020-07-24 | 江苏辉伦太阳能科技有限公司 | Reflective film layer positioned on surface of float glass and preparation method thereof |
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| CN101559979A (en) * | 2009-05-22 | 2009-10-21 | 东华大学 | Method for preparing extrafine anatase titanium dioxide nano rods |
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108465478A (en) * | 2017-02-23 | 2018-08-31 | 中国石油化工股份有限公司 | Nanoassemble mordenite catalyst and preparation method thereof |
| CN108465480A (en) * | 2017-02-23 | 2018-08-31 | 中国石油化工股份有限公司 | Special appearance mordenite catalyst and preparation method thereof |
| CN108465479A (en) * | 2017-02-23 | 2018-08-31 | 中国石油化工股份有限公司 | Self assembly special appearance mordenite catalyst and preparation method thereof |
| CN108499595A (en) * | 2017-02-23 | 2018-09-07 | 中国石油化工股份有限公司 | Special appearance mordenite catalyst |
| CN108499595B (en) * | 2017-02-23 | 2020-03-27 | 中国石油化工股份有限公司 | Mordenite catalyst with special morphology |
| CN108465479B (en) * | 2017-02-23 | 2020-03-31 | 中国石油化工股份有限公司 | Self-assembled mordenite catalyst with special morphology and preparation method thereof |
| CN108465480B (en) * | 2017-02-23 | 2020-03-31 | 中国石油化工股份有限公司 | Mordenite catalyst with special morphology and preparation method thereof |
| CN108465478B (en) * | 2017-02-23 | 2020-03-31 | 中国石油化工股份有限公司 | Nano self-assembled mordenite catalyst and preparation method thereof |
| CN111446330A (en) * | 2020-03-31 | 2020-07-24 | 江苏辉伦太阳能科技有限公司 | Reflective film layer positioned on surface of float glass and preparation method thereof |
| CN111446330B (en) * | 2020-03-31 | 2022-07-29 | 江苏辉伦太阳能科技有限公司 | Light-reflecting film layer positioned on surface of float glass and preparation method thereof |
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