CN103469291A - Method for manufacturing rutile-type titanium dioxide monocrystal nanowire arrays at normal pressure and low temperature - Google Patents
Method for manufacturing rutile-type titanium dioxide monocrystal nanowire arrays at normal pressure and low temperature Download PDFInfo
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- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title claims abstract description 98
- 239000004408 titanium dioxide Substances 0.000 title claims abstract description 40
- 238000000034 method Methods 0.000 title claims abstract description 29
- 239000002070 nanowire Substances 0.000 title abstract description 19
- 238000004519 manufacturing process Methods 0.000 title abstract description 3
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- 238000006243 chemical reaction Methods 0.000 claims abstract description 51
- FBUKVWPVBMHYJY-UHFFFAOYSA-N nonanoic acid Chemical compound CCCCCCCCC(O)=O FBUKVWPVBMHYJY-UHFFFAOYSA-N 0.000 claims abstract description 46
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000011521 glass Substances 0.000 claims abstract description 11
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- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 9
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- 239000005388 borosilicate glass Substances 0.000 claims description 5
- 239000011259 mixed solution Substances 0.000 claims description 4
- 239000004033 plastic Substances 0.000 claims description 4
- 229920003023 plastic Polymers 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
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- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 2
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- 229910000349 titanium oxysulfate Inorganic materials 0.000 claims description 2
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 claims description 2
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 claims description 2
- 239000002904 solvent Substances 0.000 abstract description 11
- 230000008859 change Effects 0.000 abstract description 5
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 abstract description 5
- 238000001308 synthesis method Methods 0.000 abstract description 3
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- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
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Abstract
The invention discloses a method for manufacturing rutile-type titanium dioxide monocrystal nanowire arrays at a normal pressure and a low temperature. The method comprises the following steps: (1) titanium source and nonoic acid are used as raw materials, are mixed uniformly according to a certain stoichiometric proportion, and are placed into a glass bottle or a Teflon reaction vessel; (2) placing a normal pressure reaction vessel into a thermostat, setting the reaction temperature at 90-220 DEG C, and the reaction time at 1-100 h, after the reaction waiting for the vessel to cool to the room temperature; (3) taking the sample in the reaction vessel, washing, and drying, so that monocrystal rutile-type nanowire arrays. Compared with the conventional synthesis method of titanium dioxide nanowire arrays which utilizes vapor pressure generated from phase change solvent as hydrothermal/solvothermal, the method provided by the invention is an environmental-friendly, safe, synthesis method at the low temperature and the normal pressure.
Description
Technical field
The present invention relates to the method that low temperature under a kind of normal pressure prepares the rutile titanium dioxide monocrystal nano line array.
Background technology
Titanium dioxide is a kind of important semiconductor material, in fields such as solar cell, photocatalysis hydrogen production, photocatalysis to degrade organic matter, lithium cell and vapor phase sensors, is widely used.The performance of titanium dioxide depends on its microscopic appearance, size and crystal formation.In the various nanostructures of having reported, single crystal titanium dioxide nanowire is because its unique one dimension electric charge transmission path can also effectively suppress the compound of electron-hole by the fast transport electronics, thereby become important object [the Zhang Q F of scientific research and industrial application, et al.Nanoscale, 2012,4,1436.Lin Y J, et al.Chemical Physics Letters2011,507,209].
The method of the synthetic single crystal titanium dioxide nano thread of having reported has template [Lei Y, et al.Appl.Phys.Lett.2001, 78, 1125], gas-liquid-solid growth [Zhuge F W, J.Phys.Chem.C2012, 116, 24367], chemical vapour deposition [Lee J – C, et al., Cryst.Growth Des., 2007, 7, 2588], organometallics chemical gaseous phase deposition [Wu J – J, et al.Phys.Chem.B, 2004, 108, 3377], magnetron sputtering [Meng L J, et al., Applied Surface Science, 2010, 256, 3676], hydrothermal method/solvent-thermal method Feng X J, et al., Nano Lett., 2008, 8, 3781.Liu B, et al., J.Am.Chem.Soc., 2009, 131, 3985].In above-mentioned synthetic method, the template synthesis complexity, first will prepare template, then by high temperature sintering or chemical corrosion, removes template, and the diameter of nano wire and length limited are in the template of selecting simultaneously.Chemical vapour deposition and gas-liquid-solid growth needs pyroreaction condition also consume a large amount of energy, and productive rate is lower.Hydrothermal method is different with the regular solution synthetic chemistry from solvent-thermal method, and in the pressurized vessel of sealing, adopting certain solvent is reaction medium, the chemical reaction that (airtight spontaneous vapour pressure) carries out under high temperature (being generally less than 250 ℃), reaction under high pressure environment.The advantage of hydro-thermal and solvent thermal synthesis method is to make reaction can at lower temperature, directly generate oxide nanocrystalline, and the metastable phase that can't obtain under normal condition before generating, avoided the high-temperature calcination processing, productive rate is high, cost low [Shi Liyi etc., China YouSe Acta Metallurgica Sinica, 2011,21,2465], and traditional technique prepares rutile and need to generate [Zhang Qinghong etc. more than 600 ℃, Journal of Inorganic Materials, 2001,16,833].Yet utilize the standby monocrystal nanowire of the hot legal system of hydrothermal/solvent to work in hyperbaric environment for a long time, due to solvent vaporize spontaneous pressure or the quick-fried still of the aging easy generation of reactor, cause danger to the person and equipment.
Therefore be necessary to develop a kind of low temperature but under condition of normal pressure the technique of safe synthesis of titanium dioxide monocrystalline gold redrock nano linear array.
Summary of the invention
The purpose of this invention is to provide a kind of method for preparing titanium dioxide single crystalline rutile type nano linear array under atmospheric low-temperature, the method technique is simple, easy handling is controlled, cost is low, pollution-free, and can be under the synthesis under normal pressure condition the safe synthesis of titanium dioxide monocrystalline of low-temp reaction rutile type nano linear array.
The present invention as unique solvent, replaces pressure influence to change the Gibbs free energy of reaction by the slow release hydrogen ions of weak acid by means of n-nonanoic acid, makes titanium dioxide nanocrystalline preferential along the growth of [001] direction.The fusing point of n-nonanoic acid is 11～12.5 ℃; boiling point is 253 ℃; therefore differently from the hydrothermal/solvent thermal response be; do not add the solvent (as water or ethanol etc.) that is produced spontaneous vapour pressure under low temperature by phase transformation in reaction; and utilize under spontaneous steam condition of high voltage and generate crystal; reaction of the present invention is that the reaction of crystallographic orientation chemistry occurs in there is no the liquid state of phase transformation; there is no reaction pressure, can be as vial with do not have directly to carry out safely synthesis under normal pressure in the polytetrafluoroethylcontainer container of stainless steel pressure casing protection.
So the core reaction reagent of utilization of the present invention is to have slow release hydrogen ions to replace pressure influence, thereby the n-nonanoic acid of the Gibbs free energy of change reaction is made solvent, and preferential edge [001] the direction generation of titanium dioxide nanocrystalline crystallographic orientation chemistry is reacted.
In addition, core reagent n-nonanoic acid used in the inventive method, another name pelargonic acid, pelargonic acid or fish pelargonium acid, be a kind of widely used organic synthesis raw material, by GB2760-96, is defined as and allows the flavouring agent used., in order to prepare coconut and berry fruit essence, be therefore mainly a kind of reagent of complete environmental protection.
Foregoing invention purpose of the present invention is achieved by the following technical solution: prepare the method for titanium dioxide single crystalline rutile type nano linear array under a kind of atmospheric low-temperature, contain following steps:
(1) get the titanium source, n-nonanoic acid stirs and obtains mixed solution;
(2) mixed solution is put into to airtight synthesis under normal pressure container, the synthesis under normal pressure container is put into to thermostat container, the conditioned reaction temperature is 90～220 ℃, and the reaction times is 1～100 hour, is cooled to room temperature after reaction;
(3) take out the sample in reaction vessel, after cleaning, drying, obtain monocrystalline rutile type nano linear array.
In step of the present invention (1), the volume ratio of titanium source, n-nonanoic acid is preferably 0.01～10mL ︰, 1～60mL.
Titanium source described in step of the present invention (1) is preferably one or more in titanium tetrachloride, titanous chloride, titanyl sulfate, butyl (tetra) titanate and isopropyl titanate.
The time of stirring in step of the present invention (1) is preferably 5min-1h.
Synthesis under normal pressure container described in step of the present invention (2) is preferably the sealed vessel that plastics or glass material are made, and different from the hydrothermal method reaction is the stainless steel casing that can not add the pressure-bearing protection.
Plastics of the present invention are preferably tetrafluoroethylene, polyimide, polybenzoate or PI polymeric amide, and described glass is preferably soda-lime glass or borosilicate glass.
Described in step of the present invention (3), cleaning to be preferably adopts deionized water and dehydrated alcohol successively to wash for several times.
Temperature while drying in step of the present invention (3) is preferably 50～70 ℃, and drying time is preferably 5～48h.
In technique scheme of the present invention, utilizing n-nonanoic acid as reaction reagent, is a kind of crystal chemistry synthetic method of atmospheric low-temperature.N-nonanoic acid is a kind of lipid acid, chemical molecular formula CH
3(CH
2)
7cOOH.In the n-nonanoic acid molecule, the carboxyl carbon atom forms 3 σ keys with alkyl and two Sauerstoffatoms respectively with the sp2 hybridized orbital, these 3 σ keys are on same plane, a remaining p electronics and Sauerstoffatom form the π key, formed the π key of C=O in the carboxyl, but in carboxyl-oxygen on the OH part has a pair of not shared electron, can form the pi-conjugated system of p-with the π key.Because p-is pi-conjugated, the electronic cloud on the Sauerstoffatom on-OH base moves to carbonyl, and the more close Sauerstoffatom of the electronic cloud between O-H makes the O-H bond polarity strengthen, be conducive to the H atom from solution.From after solving H, can suppress the hydrolysis of titanous chloride when n-nonanoic acid, make it slowly generate titanium dioxide crystal seed and carry out ordered arrangement.Simultaneously, from structural formula, hydrogen atom in n-nonanoic acid on alkyl can be large with electronegativity in titanous chloride the chlorine atom attract, along the carbochain ordered arrangement, thereby reduced the Gibbs free energy of titanium dioxide seeded growth, and the titanium source is adsorbed on the titanium dioxide nucleus from the chlorion after solution, { on the 110} face, make it preferential along the reaction of [001] direction generation crystallographic orientation chemistry.
The present invention has following advantage:
(1) in preparation method of the present invention, adopt n-nonanoic acid as unique solvent, by the slow release hydrogen ions of weak acid, replace pressure influence to change the Gibbs free energy of reaction, make titanium dioxide nanocrystalline preferential along the growth of [001] direction;
(2) solvent that adopts is n-nonanoic acid when reaction of the present invention, can not produce spontaneous vapour pressure when reaction, so, the present invention's reaction is the crystallographic orientation chemistry reaction occurred in liquid state, can the synthesis under normal pressure container as vial and polytetrafluoroethylcontainer container in safety normal-pressure reaction, reaction safety is high;
(3) the inventive method technique is simple, easy handling is controlled, cost is low, pollution-free, and can be under the synthesis under normal pressure condition low-temp reaction, with respect to tradition, utilizing reagent phase transformation generating steam to carry out the method for Hydrothermal Synthesis titanium dioxide nanowire array, is a kind of safety and environmental protection synthesis technique of normal pressure.
The accompanying drawing explanation
The XRD figure spectrum that Fig. 1 is the titanium dioxide single crystalline nano-wire array of preparation in the embodiment of the present invention 1;
The scanning electron microscope picture of titanium dioxide single crystalline nano-wire array that Fig. 2 is preparation in the embodiment of the present invention 1, the side picture of a figure nano-wire array wherein, b figure nano-wire array overlook picture;
The transmission electron microscope picture that Fig. 3 is the titanium dioxide single crystalline nano wire of preparation in the embodiment of the present invention 1, wherein a figure is the low power Electronic Speculum picture of titanium dioxide single crystalline nano wire, illustration is that corresponding surface sample is the electron-diffraction diagram of monocrystalline; B figure is the high-resolution electron microscopy picture of titanium dioxide single crystalline nano wire;
The XRD figure spectrum that Fig. 4 is the titanium dioxide single crystalline nano-wire array of preparation in the embodiment of the present invention 2;
Fig. 5 is the scanning electron microscope picture of the titanium dioxide single crystalline nano-wire array of preparation in the embodiment of the present invention 2.
Embodiment
Below in conjunction with embodiment and accompanying drawing, the present invention is further illustrated, but the scope of protection of present invention is lifted as the ratio of titanium source, temperature of reaction, reaction times and the reacted constituent of reaction unit and reaction is not limited to embodiment.
Embodiment 1
(1) measure respectively after 0.5mL titanous chloride (commercially available, lower with) and 40mL n-nonanoic acid mix and be placed on the polytetrafluoroethylcontainer container reaction unit, under normal temperature condition, use magnetic stirrer 20 minutes is standby;
(2) put in thermostat container after polytetrafluoroethylcontainer container is tightened, setting temperature of reaction is 150 ℃, and the reaction times is 12 hours, naturally cools to after completion of the reaction room temperature;
(3) after walking poly-(2) polytetrafluoroethylcontainer container and opening, taking out film cleans for several times with deionized water and dehydrated alcohol, and be placed in thermostat container under 60 ℃ of conditions and dry 24 hours, as shown in fig. 1, the crystal face diffraction peak that as can be seen from Figure 1 marked is all corresponding with the titanium dioxide of rutile phase for the XRD figure spectrum of the titanium dioxide single crystalline nano-wire array of preparation.Fig. 2 (a) and 2 (b) be respectively the titanium dioxide single crystalline nano-wire array side-view and overlook the scanning electron microscope picture, shown in Fig. 2, the array that the sample of preparation is comprised of titanium dioxide nano thread, the correspondence thickness be 9 microns.The transmission electron microscope picture of the titanium dioxide single crystalline nano-wire array of preparation as shown in Figure 3 simultaneously, Fig. 3 (a) and 3 (b) are respectively the transmission electron microscope photo of low power and high power, the diameter that can see nano wire in figure is between 10～20nm, can find out by the electron diffraction picture of corresponding Fig. 3 (a) upper left illustration the titanium dioxide nano thread that the sample of preparation is monocrystalline simultaneously.
Embodiment 2
(1) measure respectively after 0.5mL titanous chloride and 40mL n-nonanoic acid mix and be placed in the glass containers reaction unit, this Glass Containers is borosilicate glass, standby by magnetic stirrer 20 minutes under normal temperature condition;
(2) put in thermostat container after vial is tightened, setting temperature of reaction is 90 ℃, and the reaction times is 12 hours, naturally cools to after completion of the reaction room temperature;
(3) after walking poly-(2) vial and opening, taking out film cleans for several times with dehydrated alcohol and alcohol, and be placed in thermostat container under 60 ℃ of conditions and dry 24 hours, as shown in Figure 4, the crystal face diffraction peak that as can be seen from Figure 4 marked is all corresponding with the titanium dioxide of rutile phase for the XRD figure spectrum of the titanium dioxide single crystalline nano-wire array of preparation.Shown in Fig. 5 scanning electron microscope picture, the array that the sample of preparation is comprised of titanium dioxide nano thread, corresponding thickness is 3.5 μ m.
Embodiment 3
(1) measure respectively after 0.5mL titanous chloride and 40mL n-nonanoic acid mix and be placed in the glass containers reaction unit, this Glass Containers is borosilicate glass, standby by magnetic stirrer 20 minutes under normal temperature condition;
(2) put in thermostat container after vial is tightened, setting temperature of reaction is 90 ℃, and the reaction times is 12 hours, naturally cools to after completion of the reaction room temperature;
(3) after walking poly-(2) vial and opening, take out film and clean for several times with dehydrated alcohol and alcohol, and be placed in thermostat container and dry 36 hours under 50 ℃ of conditions, the array that the sample of preparation is comprised of titanium dioxide nano thread, the thickness of correspondence is 3.7 μ m.
Embodiment 4
(1) measure respectively after 0.5mL titanous chloride and 40mL n-nonanoic acid mix and be placed in the glass containers reaction unit, this Glass Containers is borosilicate glass, standby by magnetic stirrer 20 minutes under normal temperature condition;
(2) put in thermostat container after vial is tightened, setting temperature of reaction is 90 ℃, and the reaction times is 12 hours, naturally cools to after completion of the reaction room temperature;
(3) after walking poly-(2) vial and opening, take out film and clean for several times with dehydrated alcohol and alcohol, and be placed in thermostat container and dry 12 hours under 70 ℃ of conditions, the array that the sample of preparation is comprised of titanium dioxide nano thread, the thickness of correspondence is 3.6 μ m.
Embodiment 5
(1) measure respectively after 0.5mL titanous chloride and 40mL n-nonanoic acid mix and be placed in the polytetrafluoroethylcontainer container reaction unit, standby by magnetic stirrer 20 minutes under normal temperature condition;
(2) put in thermostat container after polytetrafluoroethylcontainer container is tightened, setting temperature of reaction is 90 ℃, and the reaction times is 12 hours, naturally cools to after completion of the reaction room temperature;
(3) after walking poly-(2) polytetrafluoroethylcontainer container and opening, take out film and clean for several times with dehydrated alcohol and alcohol, and be placed in thermostat container and dry 24 hours under 60 ℃ of conditions, synthetic sample is the titanium dioxide nanowire array that thickness is 4 μ m.
Above-described embodiment is preferably embodiment of the present invention; but embodiments of the present invention are not restricted to the described embodiments; other any do not deviate from change, the modification done under spirit of the present invention and principle, substitutes, combination, simplify; all should be equivalent substitute mode, be included in protection scope of the present invention.
Claims (8)
1. under a normal pressure, low temperature prepares the method for titanium dioxide single crystalline rutile type nano linear array, it is characterized in that containing following steps:
(1) get the titanium source, n-nonanoic acid stirs and obtains mixed solution;
(2) mixed solution is put into to airtight synthesis under normal pressure container, the synthesis under normal pressure container is put into to thermostat container, the conditioned reaction temperature is 90～220 ℃, and the reaction times is 1～100 hour, is cooled to room temperature after reaction;
(3) take out the sample in reaction vessel, after cleaning, drying, obtain monocrystalline rutile type nano linear array.
2. under normal pressure according to claim 1, low temperature prepares the method for titanium dioxide single crystalline rutile type nano linear array, it is characterized in that: in step (1), the volume ratio of titanium source, n-nonanoic acid is 0.01～10mL ︰, 1～60mL.
3. under normal pressure according to claim 1, low temperature prepares the method for titanium dioxide single crystalline rutile type nano linear array, and it is characterized in that: the titanium source described in step (1) is one or more in titanium tetrachloride, titanous chloride, titanyl sulfate, butyl (tetra) titanate and isopropyl titanate.
4. under normal pressure according to claim 1, low temperature prepares the method for titanium dioxide single crystalline rutile type nano linear array, it is characterized in that: the time of stirring in step (1) is 5min-1h.
5. under normal pressure according to claim 1, low temperature prepares the method for titanium dioxide single crystalline rutile type nano linear array, and it is characterized in that: synthesis under normal pressure container described in step (2) is the sealed vessel that plastics or glass material are made.
6. under normal pressure according to claim 5, low temperature prepares the method for titanium dioxide single crystalline rutile type nano linear array, it is characterized in that: described plastics are tetrafluoroethylene, polyimide, polybenzoate or PI polymeric amide, and described glass is soda-lime glass or borosilicate glass.
7. under normal pressure according to claim 1, low temperature prepares the method for titanium dioxide single crystalline rutile type nano linear array, it is characterized in that: described in step (3), clean as adopting deionized water and dehydrated alcohol successively to wash for several times.
8. under normal pressure according to claim 1, low temperature prepares the method for titanium dioxide single crystalline rutile type nano linear array, it is characterized in that: the temperature while drying in step (3) is 50～70 ℃, and drying time is 5～48h.
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Cited By (2)
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|---|---|---|---|---|
| CN107325793A (en) * | 2017-07-31 | 2017-11-07 | 河北麦森钛白粉有限公司 | A kind of phase change cold-storage composite and preparation method thereof |
| CN107936249A (en) * | 2017-12-07 | 2018-04-20 | 黑龙江科技大学 | A kind of titanium dioxide nano thread and the dielectric preparation method of polyimides composite Nano |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1986907A (en) * | 2005-12-20 | 2007-06-27 | 中国科学院兰州化学物理研究所 | Process of preparing oil soluble nano titania line |
| KR101094670B1 (en) * | 2011-08-22 | 2011-12-20 | 한국과학기술연구원 | Immobilized titanium dioxide nanowires on substrate and method for fabricating the same and water treatment method using the immobilized titanium dioxide nanowires on substrate |
| CN102383180A (en) * | 2011-10-24 | 2012-03-21 | 中山大学 | Synthesizing method for titanium dioxide single-crystal rutile nanowire array film |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1986907A (en) * | 2005-12-20 | 2007-06-27 | 中国科学院兰州化学物理研究所 | Process of preparing oil soluble nano titania line |
| KR101094670B1 (en) * | 2011-08-22 | 2011-12-20 | 한국과학기술연구원 | Immobilized titanium dioxide nanowires on substrate and method for fabricating the same and water treatment method using the immobilized titanium dioxide nanowires on substrate |
| CN102383180A (en) * | 2011-10-24 | 2012-03-21 | 中山大学 | Synthesizing method for titanium dioxide single-crystal rutile nanowire array film |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107325793A (en) * | 2017-07-31 | 2017-11-07 | 河北麦森钛白粉有限公司 | A kind of phase change cold-storage composite and preparation method thereof |
| CN107936249A (en) * | 2017-12-07 | 2018-04-20 | 黑龙江科技大学 | A kind of titanium dioxide nano thread and the dielectric preparation method of polyimides composite Nano |
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