CN102557126B - Sunlight-induced method for preparing fasciculate rutile titanium dioxide - Google Patents
Sunlight-induced method for preparing fasciculate rutile titanium dioxide Download PDFInfo
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- CN102557126B CN102557126B CN201110370588.6A CN201110370588A CN102557126B CN 102557126 B CN102557126 B CN 102557126B CN 201110370588 A CN201110370588 A CN 201110370588A CN 102557126 B CN102557126 B CN 102557126B
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Abstract
The invention discloses a sunlight-induced method for preparing fasciculate rutile titanium dioxide at room temperature. The method comprises the following steps of: forming a hydrosol by using titanium tetrachloride and water; diluting the hydrosol by adding water after the hydrosol is fully aged; obtaining a large number of white precipitates through sunlight irradiation outdoors; and filtering, washing and drying the obtained white precipitates to obtain fasciculate rutile titanium dioxide powder. The sunlight-induced method for preparing the fasciculate rutile titanium dioxide, disclosed by the invention, has the main advantages that: the crystal form of titanium dioxide is rutile, the purity of the titanium dioxide is high, and the calcination is not needed; the temperature for preparation is low, the heating is not needed, and the adding of other reagents or seed crystals is not needed; the preparation is carried out under normal pressure; only the sunlight irradiation is needed, so that the method has low carbon and energy-saving performance; and the preparation process is simple and is easy in operation.
Description
(1) technical field
The present invention relates to a kind of preparation method of sunlight induction pencil rutile titanium dioxide.
(2) background technology
Titanium dioxide (TiO
2) be the semiconductor photoelectrocatalysielectrode material of a kind of cheap, safety non-toxic and stabilizer pole, because it has good wet sensitive, pressure-sensitive, air-sensitive performance, and superior photoelectricity, dielectric effect and Photoelectrochemical stabilization, so be widely used in fields such as sensor, photoelectrocatalysis agent, makeup, high grade paint, white pigment and environmental purification.
At occurring in nature, TiO
2there are brookite, anatase octahedrite and three kinds of crystal formations of rutile.Wherein, rutile is high-temperature thermodynamics stable phase, and it has larger specific inductivity, higher specific refractory power, good ultraviolet screener performance and stronger pulverizing impedance.General rutile synthetic mainly contains two kinds of approach, and the one, by high-temperature calcination, obtain the transition process of the amorphous-anatase octahedrite-rutile of powder experience.Conventionally anatase octahedrite is 400～1000 ℃ to the transition temperature of rutile, and transition temperature and presoma, reaction conditions etc. are closely related.The 2nd, under the conditions such as certain temperature, pH, from the hydrolysate of organic titanate (salt) or inorganic titanium salt, obtain.But the former needs to experience growth, the alligatoring of crystal grain in phase transition process, and agglomeration is more serious, thereby reduced the granularity condition of sample, and calcining step has increased energy consumption; The latter, when obtaining rutile, is often accompanied by the generation of anatase octahedrite or brookite mixed crystal, and it is larger from mixed crystal, to isolate the difficulty of single crystal form, must reduce the quality of rutile, limits its industrial application.
In recent years, people show keen interest to preparing rutile titanium dioxide under cold condition.Kim Park (United States Patent (USP) the 6th, 001, No. 326) at room temperature to 65 ℃ by simple heated and stirred TiOCl
2solution has been prepared the spherical pure rutile type titanium dioxide granule that diameter is 200～400nm.Although the report of preparing aspect rutile at low temperature is both at home and abroad more, the document of directly preparing out of doors pure rutile under solar light irradiation has not yet to see report.
(3) summary of the invention
The object of the present invention is to provide a kind of low temperature, low-carbon energy-saving to prepare the novel method of rutile titanium dioxide.
For realizing the object of the invention, the technical solution adopted in the present invention is as follows:
A kind of preparation method of sunlight induction pencil rutile titanium dioxide: titanium tetrachloride and water are made to the water-sol, thin up after abundant ageing, in open air, under sunlight, expose to and occur a large amount of white precipitates, gained throw out is filtered, washs, is dried, obtain pencil rutile titanium dioxide powder.
Further, described method is preferably carried out as follows:
(a) press titanium tetrachloride and pure water by 1: 1～3 volume ratio, at 0～10 ℃ of temperature, titanium tetrachloride is added drop-wise in pure water, and fully stir, after dropwising, continuing at 0～10 ℃ of temperature and stir and make colloidal sol in 1～4 hour, under room temperature, ageing is 12 hours to 15 days;
(b) colloidal sol after the ageing of step (a) gained and pure water dilute by 1: 2～12 volume ratio, fully stir and make colourless transparent solution, in the open air of 0～40 ℃, carry out solar light irradiation 1～30 day, expose to and occur a large amount of white precipitates;
(c) by the filtration of step (b) gained throw out, filter cake washing, dry, obtain pencil rutile titanium dioxide powder.
In described step (a), the volume ratio of titanium tetrachloride and pure water is preferably 1: 2.
In described step (a), preferably at 0～5 ℃ of temperature, titanium tetrachloride is added drop-wise in pure water, and fully stirs, after dropwising, continue at 0～5 ℃ of temperature and stir and within 2 hours, make colloidal sol.
In described step (a), under room temperature, digestion time is preferably 48 hours.
In described step (a), rate of addition is conventionally controlled at 1～5mL/min, stirring velocity and is conventionally controlled at 600～1000 turn/min; Along with adding of titanium tetrachloride, the color of reaction system is transformed into oyster by water white transparency gradually, from solution, becomes colloidal sol, and the process of this solation is that those skilled in the art are known.
Pure water of the present invention can be used deionized water, medicinal water or distilled water, is all that those skilled in the art commonly use.
External temperature in described step (b) in the normal range of the temperature of open air under can keeping solution liquid phase state, does not comprise various extreme weather conditions, is generally 0～40 ℃, is preferably 10～20 ℃.
Humidity outdoor in described step (b) is also the humidity range under normal weather, does not comprise extreme weather conditions, conventionally between 10%RH～95%RH.
In described step (b), the time of solar light irradiation is preferably 20～30 days.
In described step (c), filter cake washing, dry, washs filter cake conventionally with pure water, dry in 70 ℃ of baking ovens.
Further, the preparation method of sunlight induction pencil rutile titanium dioxide of the present invention preferably carries out as follows:
(a) press the volume ratio that titanium tetrachloride and pure water are pressed 1: 2, at 0～5 ℃ of temperature, titanium tetrachloride is added drop-wise in pure water, and fully stir, continue at 0～5 ℃ of temperature and stir and make colloidal sol in 2 hours after dropwising, under room temperature, ageing is 48 hours;
(b) colloidal sol after the ageing of step (a) gained and pure water dilute by 1: 2～12 volume ratio, fully stir and make colourless transparent solution, carry out sunlight in open air, external temperature is 10～20 ℃, irradiate 20～30 days, expose to and occur a large amount of white precipitates;
(c) by the filtration of step (b) gained throw out, filter cake washing, dry, obtain pencil rutile titanium dioxide powder.
The useful technique effect of sunlight induction pencil rutile titanium dioxide technology of preparing of the present invention is mainly reflected in:
(1) crystal formation of titanium dioxide is rutile, and purity is high, and without calcining.
(2) preparation temperature is low, without heating, and does not need to add other reagent or crystal seed.
(3) normal pressure preparation.
(4) only need solar light irradiation, low-carbon energy-saving.
(5) preparation technology is simple, easy handling.
(4) accompanying drawing explanation
Fig. 1 is X-ray diffraction (XRD) figure that embodiment 1 makes rutile titanium dioxide powder.
Fig. 2 is high resolution transmission electron microscopy (HRTEM) photo that embodiment 1 makes rutile titanium dioxide powder.Wherein, Fig. 2 a is the TEM photo of the whole shape characteristic of pencil rutile; Fig. 2 b is the gathering photo of pencil rutile; Fig. 2 c and Fig. 2 d are the microstructure photos that Fig. 2 b progressively amplifies; Fig. 2 d upper right corner embedding figure is that the FEI analysis software that Fig. 2 d carries by HRTEM generates the integrally-built electron diffraction photo of pencil rutile automatically.
(5) embodiment
Below in conjunction with specific embodiment, the invention will be further described, but protection scope of the present invention is not limited to this.
Embodiment 1
(1) by a capacity, be that 500mL there-necked flask is fixed in ice-water bath, measure pure water (H
2o) 200mL packs in there-necked flask; In the middle port of there-necked flask, prolong is installed, is utilized tap water condensation; On a side mouth of there-necked flask, thermometer is installed, to monitor and to control the temperature of reaction system; Get commercially available titanium tetrachloride (TiCl
4) 100mL packs in dry dropping funnel, dropping funnel is arranged on another side mouth of there-necked flask; Under magnetic agitation and the cooling condition of ice-water bath, open the switch of dropping funnel, titanium tetrachloride solution is slowly added drop-wise in pure water, and in whole dropping process, rate of addition is controlled at the temperature that 4mL/min, stirring velocity be controlled at 800 turn/min, ice-water bath and is controlled at 0～5 ℃; Along with adding of titanium tetrachloride, the color of system is transformed into oyster by water white transparency gradually, and changes colloid into by solution; After treating that titanium tetrachloride dropwises, then continue to stir 2h, obtain 270mL colloidal sol, at room temperature place ageing 48h.
(2) measure 40mL pure water in the colourless transparent glass bottle of 100mL, then toward wherein adding the TiCl of ageing
4colloidal sol 20mL, fully stirs, and solution is colourless; Being placed on open air has the spacious place of abundant solar light irradiation, and external temperature is 10～20 ℃, and relative humidity 50～60% starts to occur a small amount of white particle after 9 days, occur a large amount of white precipitates to 30 days;
(3) gained throw out is filtered, with pure water washing, dry in 70 ℃ of baking ovens, obtain pencil rutile titanium dioxide powder 1.456g; Adopt the X ' Pert PRO type X-ray diffractometer (XRD) that Dutch PANalytical company produces that the crystalline phase of sample is formed and characterized, its XRD result as shown in Figure 1; Adopt the 300kV high resolution transmission electron microscopy (Tecnai G2 F30 S-Twin) of Dutch Philips-FEI company to characterize the shape characteristic of sample and microstructure, its TEM and HRTEM result are as shown in Figure 2.
Wherein, Fig. 2 a is the TEM photo of the whole shape characteristic of pencil rutile; Fig. 2 b is the gathering photo of pencil rutile, can find out significantly and be inheritance growth by grain; Fig. 2 c and Fig. 2 d are the microstructure photos that Fig. 2 b progressively amplifies; Fig. 2 d upper right corner embedding figure is that the FEI analysis software that Fig. 2 d carries by HRTEM generates the integrally-built electron diffraction photo of pencil rutile automatically.
As can be seen from Figure 1, phase is pure rutile type titanium dioxide, and corresponding PDF standard card number is 077-0441.
As can be seen from Figure 2, rutile is olive shape, and primary particle size scope is 3～7nm, by grain, is inheritance, pencil oriented growth; The lattice fringe that spacing of lattice is 0.32nm is simultaneously corresponding with rutile (110) oikocryst face.
Embodiment 2
(1) adopt appliance arrangement and the operation steps of step (1) in embodiment 1, by same procedure, prepare TiCl
4colloidal sol, at room temperature places ageing 48h.
(2) measure 48mL pure water in the colourless transparent glass bottle of 100mL, then toward wherein adding the TiCl of ageing
4colloidal sol 8mL, fully stirs, and solution is colourless; Being placed on open air has the spacious place of abundant solar light irradiation, and external temperature is 10～20 ℃, and relative humidity 50～60% starts to occur a small amount of white particle after 5 days, occur a large amount of white precipitates to 30 days;
(3) gained throw out is filtered, with pure water washing, dry in 70 ℃ of baking ovens, obtain pencil rutile titanium dioxide powder 0.426g.
Embodiment 3
(1) adopt appliance arrangement and the operation steps of step (1) in embodiment 1, by same procedure, prepare TiCl
4colloidal sol, at room temperature places ageing 48h.
(2) measure 48mL pure water in the colourless transparent glass bottle of 100mL, then toward wherein adding the TiCl of ageing
4colloidal sol 4mL, fully stirs, and solution is colourless; Being placed on open air has the spacious place of abundant solar light irradiation, and external temperature is 10～20 ℃, and relative humidity 50～60% starts to occur a small amount of white particle after 7 days, occur a large amount of white precipitates to 30 days;
(3) gained throw out is filtered, with pure water washing, dry in 70 ° of ℃ of baking ovens, obtain pencil rutile titanium dioxide powder 0.137g.
Comparative example 1
(1) adopt appliance arrangement and the operation steps of step (1) in embodiment 1, by same procedure, prepare TiCl
4colloidal sol, at room temperature places ageing 48h.
(2) measure 40mL pure water in the colourless transparent glass bottle of 100mL, then toward wherein adding the TiCl of ageing
4colloidal sol 20mL, fully stirs, and solution is colourless; Be placed on indoor lucifuge place, room temp is 10～20 ℃, and relative humidity 50～60% did not occur white precipitate in 50 days.
Comparative example 2
(1) adopt appliance arrangement and the operation steps of step (1) in embodiment 1, by same procedure, prepare TiCl
4colloidal sol, at room temperature places ageing 48h.
(2) measure 48mL pure water in the colourless transparent glass bottle of 100mL, then toward wherein adding the TiCl of ageing
4colloidal sol 8mL, fully stirs, and solution is colourless; Be placed on indoor lucifuge place, room temp is 10～20 ℃, and relative humidity 50～60% did not occur white precipitate in 50 days.
Comparative example 3
(1) adopt appliance arrangement and the operation steps of step (1) in embodiment 1, by same procedure, prepare TiCl
4colloidal sol, at room temperature places ageing 48h.
(2) measure 48mL pure water in the colourless transparent glass bottle of 100mL, then toward wherein adding the TiCl of ageing
4colloidal sol 4mL, fully stirs, and solution is colourless; Be placed on indoor lucifuge place, room temp is 10～20 ℃, and relative humidity 50～60% did not occur white precipitate in 50 days.
Claims (7)
1. a sunlight is induced the preparation method of pencil rutile titanium dioxide, it is characterized in that described method is: titanium tetrachloride and water are made to the water-sol, thin up after abundant ageing, in open air, under sunlight, expose to and occur a large amount of white precipitates, gained throw out is filtered, washs, is dried, obtain pencil rutile titanium dioxide powder;
Described method is carried out as follows:
(a) press the volume ratio that titanium tetrachloride and pure water are pressed 1:1～3, at 0～10 ℃ of temperature, titanium tetrachloride is added drop-wise in pure water, and fully stir, after dropwising, continuing at 0～10 ℃ of temperature and stir and make colloidal sol in 1～4 hour, under room temperature, ageing is 12 hours to 15 days;
(b) the volume ratio dilution that the colloidal sol after the ageing of step (a) gained and pure water are pressed 1:2～12, fully stirs and makes colourless transparent solution, in the open air of 0～40 ℃, carries out solar light irradiation 1～30 day, exposes to and occurs a large amount of white precipitates;
(c) by the filtration of step (b) gained throw out, filter cake washing, dry, obtain pencil rutile titanium dioxide powder.
2. the preparation method of sunlight induction pencil rutile titanium dioxide according to claim 1, is characterized in that, in described step (a), the volume ratio of titanium tetrachloride and pure water is 1:2.
3. sunlight according to claim 1 is induced the preparation method of pencil rutile titanium dioxide, it is characterized in that in described step (a), at 0～5 ℃ of temperature, titanium tetrachloride is added drop-wise in pure water, and fully stir, after dropwising, continue at 0～5 ℃ of temperature and stir and within 2 hours, make colloidal sol.
4. the preparation method of sunlight induction pencil rutile titanium dioxide according to claim 1, is characterized in that, in described step (a), under room temperature, ageing is 48 hours.
5. the preparation method of sunlight induction pencil rutile titanium dioxide according to claim 1, is characterized in that in described step (b), and outdoor temperature is 10～20 ℃.
6. the preparation method of sunlight induction pencil rutile titanium dioxide according to claim 1, is characterized in that, in described step (b), the time of solar light irradiation is 20～30 days.
7. the preparation method of sunlight according to claim 1 induction pencil rutile titanium dioxide, is characterized in that described method carries out as follows:
(a) press the volume ratio that titanium tetrachloride and pure water are pressed 1:2, at 0～5 ℃ of temperature, titanium tetrachloride is added drop-wise in pure water, and fully stir, continue at 0～5 ℃ of temperature and stir and make colloidal sol in 2 hours after dropwising, under room temperature, ageing is 48 hours;
(b) the volume ratio dilution that the colloidal sol after the ageing of step (a) gained and pure water are pressed 1:2～12, fully stirs and makes colourless transparent solution, carries out sunlight in open air, and external temperature is 10～20 ℃, irradiates 20～30 days, exposes to and occurs a large amount of white precipitates;
(c) by the filtration of step (b) gained throw out, filter cake washing, dry, obtain pencil rutile titanium dioxide powder.
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| CN1390889A (en) * | 2001-06-08 | 2003-01-15 | 中国科学院化学研究所 | Process for preparing rutile-type titanium oxide powder |
| CN1459331A (en) * | 2002-05-21 | 2003-12-03 | 中国科学院化学研究所 | Prepn. method for producing titanium dioxide having visible light catalytic activation |
| CN1631795A (en) * | 2004-11-16 | 2005-06-29 | 浙江工业大学 | Process for preparing rutile phase titanium dioxide nano-powder |
| CN1834021A (en) * | 2006-04-07 | 2006-09-20 | 浙江工业大学 | Prepn. process of mesic hole hollow ball-shape titania powder |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1390889A (en) * | 2001-06-08 | 2003-01-15 | 中国科学院化学研究所 | Process for preparing rutile-type titanium oxide powder |
| CN1459331A (en) * | 2002-05-21 | 2003-12-03 | 中国科学院化学研究所 | Prepn. method for producing titanium dioxide having visible light catalytic activation |
| CN1631795A (en) * | 2004-11-16 | 2005-06-29 | 浙江工业大学 | Process for preparing rutile phase titanium dioxide nano-powder |
| CN1834021A (en) * | 2006-04-07 | 2006-09-20 | 浙江工业大学 | Prepn. process of mesic hole hollow ball-shape titania powder |
Non-Patent Citations (2)
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| light-induced formation of porous TiO2 with superior electron-storing capacity;Xiao-Xin Zou et.al;《Chem. Commun.》;20101231(第46期);2112-2114 * |
| Xiao-Xin Zou et.al.light-induced formation of porous TiO2 with superior electron-storing capacity.《Chem. Commun.》.2010,(第46期),2112-2114. |
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Inventor after: Li Guohua Inventor after: Zhang Xuanhui Inventor after: Ren Xiaoqing Inventor before: Li Guohua Inventor before: Zhang Xuanhui |
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