CN103539202B - Method for preparing titanium dioxide nanowire through self-reaction of single reagent - Google Patents
Method for preparing titanium dioxide nanowire through self-reaction of single reagent Download PDFInfo
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- CN103539202B CN103539202B CN201310373400.2A CN201310373400A CN103539202B CN 103539202 B CN103539202 B CN 103539202B CN 201310373400 A CN201310373400 A CN 201310373400A CN 103539202 B CN103539202 B CN 103539202B
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Abstract
The invention discloses a method for preparing a titanium dioxide nanowire through self-reaction of a single reagent. The method comprises the following steps: (1) taking a titanium trichloride solution as an initial raw material, placing the titanium trichloride solution in a hydrothermal reaction kettle, placing in a thermostat, adjusting the reaction temperature to be 90-230 DEG C, and cooling to room temperature after reaction, wherein the reaction time is 1-100 hours; and (2) taking a sample out of the reaction kettle, cleaning and drying to obtain the titanium dioxide nanowire. The method has the advantages of simple process, easiness in operation and control, low cost, safety and environmental friendliness.
Description
Technical field
The present invention is specifically related to a kind of method that single agents autoreaction prepares titanium dioxide nano thread.
Background technology
As the n-type semiconductor of broad-band gap (3.1eV), titanium dioxide has obtained further investigation and widespread use in fields such as lithium cell, photochemical catalysis, dye-sensitized solar cells.Titanium dioxide one dimension Nano structure such as nano wire, nanotube and nanometer sheet etc. have attracted great concern due to its special optical, electrical, magnetic, chemistry and mechanical characteristics etc.Such as nano wire, in above-mentioned application, can provide the passage of the electric transmission of one dimension, thus the recombination losses of fast transport electronics and reduction electron-hole.
The method of the synthesis of titanium dioxide nano wire reported has electron beam evaporation [Yang T S, et al.Surf Sci, 2004, 548:75], synthesis method [Adachi M assisted by tensio-active agent, et al., J Am Chem Soc, 2004, 126:14943], electricity spraying method [Song M Y, et al., Appl Phys Lett, 2005, 87:113113], electrodip process [Natarajan C, et al.J Electrochem Soc, 1996, 143:1547], highly basic hydrothermal method [Enache-Pommer E, et al., Appl.Phys.Lett.2007, 91:123116.] and hydrochloric acid hydrothermal method [Liu B.et al., J.Am.Chem.Soc.2009, 131:3985].In the above-mentioned methods hydrothermal method due to cost relatively low, productive rate height is a kind of method of extensive research.Wherein highly basic hydrothermal method first generates sodium titanate by titanium source and highly basic (NaOH or KOH), then carry out ion-exchange with hydrochloric acid to generate metatitanic acid, and final high temperature calcining generates titanium dioxide nano thread, and step is poly-complicated.In addition, hydrochloric acid hydrothermal method is in synthesis, add titanium source and hydrochloric acid water thermal response, hydrochloric acid suppresses the fast hydrolyzing in titanium source on the one hand, and another aspect provides chlorion to be adsorbed on { on 110} face, making its [001] direction, preferential edge that crystallographic orientation chemistry occur and reacting of titanium dioxide nucleus.Above-mentioned technique have employed strong acid and highly basic, and also step is complicated relatively for highly basic hydrothermal method simultaneously.Therefore be necessary to develop a kind of new technique simple, with low cost and be easy to realize the preparation technology of suitability for industrialized production.
Summary of the invention
Technical problem to be solved by this invention is to provide a kind of method that single agents autoreaction prepares titanium dioxide nano thread, and the method technique is simple, easy handling controls, cost is low, safety and environmental protection.
Above-mentioned technical problem of the present invention is achieved by the following technical solution: a kind of single agents autoreaction prepares the method for titanium dioxide nano thread, containing following steps:
(1) get Titanium Trichloride Solution as starting raw material, Titanium Trichloride Solution is put into hydrothermal reaction kettle, then puts into thermostat container, regulate temperature of reaction to be 90 ~ 230 DEG C, the reaction times is 1 ~ 100 hour, is cooled to room temperature after reaction;
(2) take out the sample in reactor, after cleaning, oven dry, obtain titanium dioxide nano thread.
In step of the present invention (1), the mass percentage of Titanium Trichloride Solution is preferably 8% ~ 30%, and Titanium Trichloride Solution volume preferably accounts for 5% ~ 80% of reactor cumulative volume.
Hydrothermal reaction kettle described in step of the present invention (1) is preferably airtight high-temperature high-pressure reaction kettle, and described high-temperature high-pressure reaction kettle has metal shell, is preferably provided with heat-resisting and corrosion-resistant plastic or glass-lined in metal shell.
Heat-resisting and corrosion-resistant plastic of the present invention is preferably tetrafluoroethylene, polyimide, polybenzoate or PI polymeric amide.
In order to better generate titanium dioxide nanowire array, in step of the present invention (1), supine conductive glass can be set in Polycondensation Reactor and Esterification Reactor.Wherein conductive glass can be FTO conductive glass (SnO
2mix F) etc.
In step of the present invention (2), cleaning is preferably and adopts deionized water and dehydrated alcohol successively to wash for several times.
Temperature when drying in step of the present invention (2) is preferably 50 ~ 70 DEG C, and drying time is preferably 5 ~ 48h.
The core of the preparation method of titanium dioxide nano thread of the present invention generates titanium dioxide nano thread after there is hydro-thermal reaction by means of titanous chloride single agents self, the Titanium Trichloride Solution (not making any dilution or concentration) produced using genuine is as starting raw material, Titanium Trichloride Solution is put into hydrothermal reaction kettle, hydrothermal reaction kettle is put into isothermal reaction case to react, after reaction terminates, hydrothermal reaction kettle is naturally cooled to room temperature, after being dried by obtained sample clean, titanium dioxide nano thread sample can be obtained.
In the preparation method of titanium dioxide nano thread of the present invention, core reagent Titanium Trichloride Solution used, can be there is hydrolysis generation titanium dioxide nucleus in titanous chloride under hydrothermal conditions, there are hydrogen ion and chlorion product to generate simultaneously, thus avoid the hydrochloric acid that adds in traditional technology, the hydrogen ion of dissociation suppresses the fast hydrolyzing of titanous chloride to generate unbodied titanium dioxide, and the chlorion of dissociation is adsorbed onto { on 110} face, making its [001] direction, preferential edge that crystallographic orientation chemistry occur and reacting of titanium dioxide nucleus.Therefore the preparation method of titanium dioxide nano thread of the present invention can be realized the generation of nano wire by the Titanium Trichloride Solution of single agents.
Tool of the present invention has the following advantages:
(1) preparation method of the present invention, adopts Titanium Trichloride Solution as single agents, and the hydrogen ion generated by titanous chloride self hydrolysis and chlorion replace the hydrochloric acid added in traditional technology, thus realizes single agents autoreaction generation titanium dioxide nano thread;
(2) preparation method of the present invention generates titanium dioxide nano thread by single agents autoreaction, and the proportioning avoiding reagent in operating process weighs, and therefore the method technique is simple, easy handling controls, cost is low;
(3) preparation method of the present invention compares with the technique of highly basic with the strong acid used of traditional technology in document, avoid strong acid and highly basic and the potentially dangerous and healthy effect that strong acid and highly basic causes the person is contacted in operation to staff, simultaneously relatively easy to reacted liquid waste disposal, so preparation method of the present invention is a kind of safety and environmental protection synthesis technique;
(4) preparation method of the present invention is relative to the method for tradition highly basic or strong acid Hydrothermal Synthesis titanium dioxide nano thread, avoid strong acid and highly basic to the stainless corrosion damage of reactor shell and the damage of leaking in reaction process stove, be conducive to the cost depletions of minimizing equipment.
Accompanying drawing explanation
Fig. 1 is the XRD figure spectrum of the titanium dioxide nano thread of preparation in the embodiment of the present invention 1;
Fig. 2 is the scanning electron microscopic picture of the titanium dioxide nano thread of preparation in the embodiment of the present invention 1;
Fig. 3 is the scanning electron microscopic picture of the titanium dioxide nano thread of preparation in the embodiment of the present invention 2, and (a) is corresponding low range picture, and (b) is corresponding high magnification picture;
Fig. 4 is the scanning electron microscopic picture of the titanium dioxide nano thread of preparation in the embodiment of the present invention 3, and wherein (a) is corresponding low range picture, and (b) is corresponding high magnification picture;
Fig. 5 is the scanning electron microscopic picture of the titanium dioxide nano thread of preparation in the embodiment of the present invention 4, and wherein (a) is corresponding low range picture, and (b) is corresponding high magnification picture;
Fig. 6 is the scanning electron microscopic picture of the titanium dioxide nano thread of preparation in the embodiment of the present invention 5, and wherein (a) is corresponding low range picture, and (b) is corresponding high magnification picture.
Embodiment
Below in conjunction with embodiment and accompanying drawing, the present invention is further illustrated, but the volume of the scope of protection of present invention as reaction unit and temperature of reaction, reaction times and reaction liquid be not limited to embodiment lifted.
Embodiment 1
(1) (manufacturer is Chemical Reagent Co., Ltd., Sinopharm Group to measure 5mL Titanium Trichloride Solution, mass percentage is 15 ~ 20%) without any dilution or concentrated be placed in 100mL reactor, conductive glass conducting surface is placed on Polycondensation Reactor and Esterification Reactor induced nano line oriented growth upward, reactor is airtight high-temperature high-pressure reaction kettle, high-temperature high-pressure reaction kettle has metal shell, plastics or glass-lined is provided with in metal shell, wherein plastics are tetrafluoroethylene, polyimide, the materials such as polybenzoate or PI polymeric amide, following examples are same, then put into after reactor being tightened in thermostat container, setting temperature of reaction is 150 DEG C, reaction times is 12 hours, naturally cool to room temperature after completion of the reaction,
(2) after poly-for step (2) reactor being opened, take out the film deionized water and washes of absolute alcohol several that are deposited on conductive glass, and to be placed in thermostat container under 60 DEG C of conditions and to dry 24 hours, the diffraction peak that the sample of synthesis is marked by Fig. 1 is all corresponding with titanium dioxide Rutile Type, by Fig. 2, the sample of synthesis can see that the thickness for being made up of the nano wire of diameter 7 ~ 20 nanometer is about 2.8 hum silicon dioxide titanium nano-wire arrays.
Embodiment 2
(1) (manufacturer is Chemical Reagent Co., Ltd., Sinopharm Group to measure 15mL Titanium Trichloride Solution, mass percentage is 15 ~ 20%) be placed in 100mL reactor, conductive glass conducting surface is placed on Polycondensation Reactor and Esterification Reactor induction admittance rice noodles oriented growth upward, then put into after reactor being tightened in thermostat container, setting temperature of reaction is 150 DEG C, reaction times is 12 hours, naturally cools to room temperature after completion of the reaction;
(2) after step (1) reactor being opened, take out the film deionized water and washes of absolute alcohol several that are deposited on conductive glass, and to be placed in thermostat container under 70 DEG C of conditions and to dry 12 hours, by Fig. 3 (a), the sample of synthesis can see that the thickness formed for nano wire is about 4 hum silicon dioxide titanium nano-wire arrays, can be seen the nanometer bundle be made up of the nano wire of diameter 6 ~ 10nm by Fig. 3 (b).
Embodiment 3
(1) (manufacturer is Aladdin reagent (Shanghai) Co., Ltd. to measure 15mL Titanium Trichloride Solution, mass percentage is 15 ~ 20%) be placed in 100mL reactor, not putting conductive glass as different from Example 1 makes nano wire without array orientation induced growth, then put into after reactor being tightened in thermostat container, setting temperature of reaction is 150 DEG C, reaction times is 12 hours, naturally cools to room temperature after completion of the reaction;
(2) after step (1) reactor being opened, take out sample deionized water and washes of absolute alcohol several, and to be placed in thermostat container under 60 DEG C of conditions and to dry 24 hours, can find out that diameter that the nano wire that sample is about 6 ~ 10nm by diameter forms is the micron ball of 5 ~ 10 microns by Fig. 4 (a) and (b) low power and high power picture.
Embodiment 4
(1) (manufacturer is Chemical Reagent Co., Ltd., Sinopharm Group to measure 30mL Titanium Trichloride Solution, mass percentage is 15 ~ 20%) be placed in 100mL reactor, not putting conductive glass as different from Example 1 makes nano wire without array orientation induced growth, then put into after reactor being tightened in thermostat container, setting temperature of reaction is 150 DEG C, reaction times is 12 hours, naturally cools to room temperature after completion of the reaction;
(2) after step (1) reactor being opened, take out sample deionized water and washes of absolute alcohol several, and to be placed in thermostat container under 50 DEG C of conditions and to dry 24 hours, the micron ball of the diameter 1 ~ 10 micron that the nano wire that sample is about 6 ~ 10nm by diameter forms can be found out by Fig. 5 (a) and (b) low power and high power picture.
Embodiment 5
(1) (manufacturer is SIGMA-ALDRICH to measure 40mL Titanium Trichloride Solution, mass percentage is 12%) be placed in 100mL reactor, not putting conductive glass as different from Example 1 makes nano wire without array orientation induced growth, then put into after reactor being tightened in thermostat container, setting temperature of reaction is 200 DEG C, reaction times is 12 hours, naturally cools to room temperature after completion of the reaction;
(2) after step (1) reactor being opened, take out sample deionized water and washes of absolute alcohol several, and to be placed in thermostat container under 60 DEG C of conditions and to dry 24 hours, the sample of synthesis can see by Fig. 6 (a) micron ball that titanium dioxide nano thread forms, and become the aggregate of nano wire due to stress fracture, can see that the diameter of nano wire is about 10 ~ 20nm by Fig. 6 (b).
Above-described embodiment is the present invention's preferably embodiment; but embodiments of the present invention are not restricted to the described embodiments; change, the modification done under other any does not deviate from spirit of the present invention and principle, substitute, combine, simplify; all should be the substitute mode of equivalence, be included in protection scope of the present invention.
Claims (2)
1. single agents autoreaction prepares a method for titanium dioxide nano thread, it is characterized in that containing following steps:
(1) get Titanium Trichloride Solution as starting raw material, Titanium Trichloride Solution is put into hydrothermal reaction kettle, then puts into thermostat container, regulate temperature of reaction to be 90 ~ 230 DEG C, the reaction times is 1 ~ 100 hour, is cooled to room temperature after reaction;
(2) take out the sample in reactor, after cleaning, oven dry, obtain titanium dioxide nano thread;
In step (1), the mass percentage of Titanium Trichloride Solution is 8% ~ 30%.
2. single agents autoreaction according to claim 1 prepares the method for titanium dioxide nano thread, it is characterized in that: Titanium Trichloride Solution volume accounts for 5% ~ 80% of reactor cumulative volume.
3. single agents autoreaction according to claim 1 prepares the method for titanium dioxide nano thread, it is characterized in that: described in step (1), hydrothermal reaction kettle is airtight high-temperature high-pressure reaction kettle, described high-temperature high-pressure reaction kettle has metal shell, is provided with heat-resisting and corrosion-resistant plastic or glass-lined in metal shell.
4. single agents autoreaction according to claim 3 prepares the method for titanium dioxide nano thread, it is characterized in that: described heat-resisting and corrosion-resistant plastic is tetrafluoroethylene, polyimide or polybenzoate.
5. single agents autoreaction according to claim 1 prepares the method for titanium dioxide nano thread, it is characterized in that: in step (2), cleaning is successively washed for several times for adopting deionized water and dehydrated alcohol.
6. single agents autoreaction according to claim 1 prepares the method for titanium dioxide nano thread, it is characterized in that: temperature when drying in step (2) is 50 ~ 70 DEG C, and drying time is 5 ~ 48h.
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| CN104229879A (en) * | 2014-09-02 | 2014-12-24 | 陈立晓 | Preparation method of rutile titanium dioxide nano powder |
| CN104528754B (en) * | 2014-11-17 | 2016-08-24 | 山东玉皇新能源科技有限公司 | A kind of nano bar-shape AlPO4the synthetic method of-15 |
| CN105006370A (en) * | 2015-06-23 | 2015-10-28 | 南京航空航天大学 | Method for in-situ preparing CZTS counter electrode by means of solvent thermal and application of CZTS counter electrode |
| CN108264087B (en) * | 2018-03-16 | 2020-05-05 | 中国科学院广州地球化学研究所 | Single reagent self-reaction preparation of Nb with directional arrangement2O5Method for producing nano-rod |
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