CN102963926A - Method for preparing mixed crystal type titanium dioxide nano-powder and product thereof - Google Patents
Method for preparing mixed crystal type titanium dioxide nano-powder and product thereof Download PDFInfo
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- CN102963926A CN102963926A CN2012104028172A CN201210402817A CN102963926A CN 102963926 A CN102963926 A CN 102963926A CN 2012104028172 A CN2012104028172 A CN 2012104028172A CN 201210402817 A CN201210402817 A CN 201210402817A CN 102963926 A CN102963926 A CN 102963926A
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Abstract
The invention discloses a method for preparing mixed crystal type titanium dioxide nano-powder containing anatase and rutile. The method comprises: (a) hydrolyzing and precipitating tetrabutyl titanate or titanium isopropoxide, and mixing the formed precipitate and nitric acid to form a titanium salt solution; (b) adding urea into the prepared titanium salt solution to form a mixed solution, with a mole ratio of the urea and the titanium ion in the titanium salt solution being 0.4 to 40; and (c) performing a self-propagating combustion for the mixed solution in a high-temperature furnace of 300 to 600 DEG C, so as to obtain a mixed crystal type titanium dioxide nano-powder simultaneously containing anatase and rutile. The invention further discloses corresponding preparation product. According to the invention, the nanoscale titanium dioxide powder can be obtained with simple process and low cost; and the prepared product simultaneously contains the anatase and the rutile, is small in grain size, uniform in granularity and excellent in photocatalytic degradation.
Description
Technical field
The invention belongs to the photocatalyst material technical field, more specifically, relate to method of a kind of mixing crystal formation titanic oxide nano powder for the preparation of comprising Detitanium-ore-type and rutile-type and products thereof.
Background technology
TiO
2Because have that oxidation capacity is strong, degraded thoroughly, non-secondary pollution, good, the low cost and other advantages of chemical stability, become the most a kind of photocatalyst of studying over nearly 40 years, be widely applied in the photocatalysis field such as photodissociation water, carbon nitrogen are fixed, degradation of organic substances.TiO
2Photocatalytic activity and its crystal formation, degree of crystallinity, pattern, granular size closely related.TiO
2Comprise Anatase, Rutile Type and three kinds of crystalline structures of brookite, studies show that the TiO of Anatase and Rutile Type
2All have photocatalytic activity, and contain the TiO that two-phase (Anatase and Rutile Type) is mixed crystal formation
2Then has higher photocatalysis performance.Correspondingly, need badly in the reality and seek a kind of mode of can be with simple process, low cost, being easy to control quality product and prepare and mix crystal formation TiO
2Processing method.
The method that at present relevant preparation comprises above-mentioned mixing crystal formation titanium dioxide mainly is to adopt sol-gel method, hydrothermal method or microemulsion method.These preparation methods generate by control calcining temperature or interpolation foreign ion to include simultaneously Detitanium-ore-type and rutile TiO
2Mixing crystal formation product, yet these existing preparation methods' defective is: (1) complex process, be difficult to its processing condition are carried out accurately control, the corresponding quality stability that obtains product is not high; (2) the special calciner of calcination processing process need, and reaction time consumption is long, and formation efficiency is not high, is difficult to adapt to the Production requirement of extensive batch; (3) no matter control reaction process owing to need to add foreign ion, be addition or interpolation time all to be difficult to accurate control, and cost is high, and be easy to introduce other inevitable impurity, affects the quality of the finished product.Therefore, exist in this area mixing the further improved technical need of crystal formation titania powder preparation technology.Exist mixing the further improved technical need of crystal formation titanium dioxide preparation technology in field of photocatalytic material.
Summary of the invention
Above defective and technical need for prior art, the object of the present invention is to provide method of a kind of mixing crystal formation titanic oxide nano powder for the preparation of comprising Detitanium-ore-type and rutile-type and products thereof, it is by studying and improve at aspects such as committed step thing and reaction conditionss thereof, can technique obtain simply, inexpensively the nano level product, and be convenient to control quality and be suitable for large-scale mass production; Prepared mixing crystal formation titanic oxide nano powder grain-size is little, and epigranular comprises two kinds of structures of Detitanium-ore-type and rutile-type simultaneously, and shows excellent photocatalytic degradation ability.
According to one aspect of the present invention, a kind of method of the mixing crystal formation titanic oxide nano powder for the preparation of comprising Detitanium-ore-type and rutile-type is provided, it is characterized in that the method comprises the following steps:
(a) tetrabutyl titanate or titanium isopropylate are joined form white precipitate in the deionized water, separate this white precipitate and washes clean, and then be distributed in the deionized water, and to drip while stirring concentration be 40% ~ 63% nitric acid, makes transparent titanium salt solution after fully stirring;
(b) add in the prepared titanium salt solution as the urea of reductive agent and fuel forming mixing solutions, and the mol ratio between the titanium ion in this urea and the described titanium salt solution is 0.4-4.0;
(c) place 300 ℃-600 ℃ High Temperature Furnaces Heating Apparatus to carry out self-propagating combustion the formed mixing solutions of step (b), obtain to include simultaneously thus the mixing crystal formation titanic oxide nano powder of Detitanium-ore-type and two kinds of structures of rutile-type.
By above design, first tetrabutyl titanate or titanium isopropylate hydrolysis are formed precipitation on the one hand, to be precipitated and dissolved in again and form nitrate in the nitric acid, this nitrate is directly as oxygenant, can a direct step generate titanium dioxide product with reductive agent urea by oxidation-reduction reaction, save the high-temperature calcination treating processes, simple to operate; On the other hand, this reaction process is a fast self-propagating combustion building-up process, and the whole building-up process time is short, is several minutes only, is conducive to reduce the integral production cost, the controllability of improving the quality of products.
As further preferably, in step (b), the mol ratio between the titanium ion in described urea and the titanium salt solution is 0.45-2.5.
In the burning synthetic system take urea as organic-fuel, there is important impact in the factors such as raw material stoicheiometry, pH value, ignition temperature for reaction process and product quality.By the mol ratio between the titanium ion in urea and the titanium salt solution further specifically is defined as above scope, more simultaneous test shows: its ratio of components can guarantee the self-propagating combustion of mixing solutions, and obtain little, the even-grained nano level product of grain-size, and its powder total quality is better.
As further preferably, in step (c), when adopting urea to act as a fuel, the ignition temperature of carrying out described self-propagating combustion is about 500 ℃.
As further preferably, in step (b), can also adopt glycine or citric acid to replace described urea, and the mol ratio between the titanium ion in itself and the titanium salt solution is 0.5-1.5.
By adopting glycine or citric acid to replace urea as organic-fuel, can be at the clean-burning consumption that reduces simultaneously organic-fuel that guarantees mixing solutions, and in the oxidation-reduction process of mixing solutions, play the effect of reductive agent.In addition, take glycine or citric acid in the burning synthetic system of organic-fuel, more simultaneous test shows, by the mol ratio between this organic-fuel and the titanium ion specifically is defined as above scope, its ratio of components can guarantee the self-propagating combustion of mixing solutions, and its powder quality is better.
As further preferably, in step (b), add in the described titanium salt solution in the process of described fuel and carry out magnetic agitation.
As further preferably, in step (c), when adopting glycine or citric acid to act as a fuel, the ignition temperature of carrying out described self-propagating combustion is about 600 ℃.
According to another aspect of the present invention, also provide corresponding mixing crystal formation titanic oxide nano powder product.
As further preferably, the particle diameter mean sizes of described mixing crystal formation titanic oxide nano powder product is about 15nm-150nm.
In general, according to method of the mixing crystal formation titanic oxide nano powder for the preparation of comprising Detitanium-ore-type and rutile-type of the present invention and products thereof compared with prior art, mainly possess following technological merit:
1, improve by preparation being mixed the aspects such as committed step thing in the crystal formation titania powder process and reaction conditions thereof, can relative amplitude ground increase production efficiency, and improve the quality of products controlled; In addition, the self-propagating combustion mode is faster with calcination processing mode phase specific rate, and can avoid the introducing of foreign ion, and therefore energy-conservation and reduction cost is particularly useful for large batch of scale production;
2, by to adding organic-fuel type and the condition such as raw material stoicheiometry ignition temperature study, improve the speed of reaction of burning synthetic system when can guarantee the abundant self-propagating combustion of mixing solutions, and possess preferably nano-powder of quality;
3, little according to the prepared mixing crystal formation of the present invention titanic oxide nano powder product grains size, epigranular, the particle diameter mean sizes is about 15nm-150nm, comprises simultaneously two kinds of structures of Detitanium-ore-type and rutile-type, and shows excellent photocatalytic degradation ability.
Description of drawings
Fig. 1 is according to the process flow sheet for the preparation of mixing the crystal formation titanic oxide nano powder of the present invention;
Fig. 2 is the scanning electron microscope (SEM) photograph according to the embodiment of the invention 1 prepared 1# sample;
Fig. 3 is the scanning electron microscope (SEM) photograph according to the embodiment of the invention 2 prepared 2# samples;
Fig. 4 is the scanning electron microscope (SEM) photograph according to the embodiment of the invention 3 prepared 3# samples;
Fig. 5 is the scanning electron microscope (SEM) photograph according to the embodiment of the invention 4 prepared 4# samples;
Fig. 6 carries out the XRD figure spectrum that test forms to above 1#-4# sample;
Fig. 7 adopts methyl orange solution to carry out the degradation rate synoptic diagram of test to above 1#-4# sample.
Embodiment
In order to make purpose of the present invention, technical scheme and advantage clearer, below in conjunction with drawings and Examples, the present invention is further elaborated.Should be appreciated that specific embodiment described herein only in order to explain the present invention, is not intended to limit the present invention.In addition, below in each embodiment of described the present invention involved technical characterictic just can mutually not make up as long as consist of each other conflict.
Fig. 1 is the process flow sheet that comprises the mixing crystal formation titanic oxide nano powder of Detitanium-ore-type and rutile-type according to of the present invention.As shown in fig. 1, in order to prepare the mixing crystal formation titanic oxide nano powder that includes simultaneously Detitanium-ore-type and two kinds of structures of rutile-type, at first, the tetrabutyl titanate of the certainweight of weighing or titanium isopropylate join in the solvent of deionized water for example, and form white precipitate; The white precipitate that forms is separated and adopt deionized water wash clean, and then to be distributed in the deionized water and to drip while stirring concentration be 40% ~ 63% nitric acid, make transparent titanium salt solution after fully stirring.
Then, in prepared titanium salt solution, the urea of weighing certainweight (also can adopt glycine or citric acid to replace), and it is added to go in the titanium salt solution and carry out magnetic agitation to form mixing solutions, wherein when adding urea, mol ratio in itself and the titanium salt solution between the titanium ion is 0.4-4.0, is preferably 0.45-2.5; And when adding glycine or citric acid, the mol ratio in itself and the titanium salt solution between the titanium ion is 0.5-1.5.Acting as the synthetic organic-fuel of follow-up self-propagating combustion, simultaneously also as the reductive agent in chemical oxidation-reduction reaction system of urea or similar substance.
Then, place 300 ℃-600 ℃ High Temperature Furnaces Heating Apparatus to consist of the burning synthetic system the formed mixing solutions of above step, and utilize above-mentioned organic-fuel to carry out self-propagating combustion; Condition down-firing about 500 ℃, the mixing solutions self-propagating combustion, acquisition includes the mixing crystal formation titanic oxide nano powder of Detitanium-ore-type and two kinds of structures of rutile-type simultaneously thus.
Show that after tested the particle diameter of prepared mixing crystal formation titanic oxide nano powder product is 15nm-150nm.
Take by weighing the tetrabutyl titanate of 10.20g, adding an amount of deionized water makes the tetrabutyl titanate complete hydrolysis obtain white precipitate, separate this white precipitate and with deionized water with its washes clean, then after adding the 30mL deionized water in the precipitation, while stirring to the concentrated nitric acid that wherein slowly drips about 20mL, fully stirring is dissolved precipitation fully, obtains the solution of clear; Add again weight range in the solution and can be controlled in the urea of 0.72g-7.2g and suitable deionized water (in the present embodiment, specifically having added the urea of 0.81g and an amount of deionized water), form the clear mixing solutions of 100ml after the magnetic agitation; Above-mentioned mixing solutions is placed 350 ℃ High Temperature Furnaces Heating Apparatus, and violent combustion reactions occurs, the complete rear acquisition puffy powder of combustion reactions in solution after evaporation, boiling and bubbling.This powder is ground with mortar, obtain the 1# sample.
Fig. 2 is the scanning electron microscope (SEM) photograph according to the embodiment of the invention 1 prepared 1# sample, and as seen from the figure, the size distribution of 1# sample is comparatively even, and particle size is less, and median size is about 15nm.
Take by weighing the titanium isopropylate of 8.53g, adding an amount of deionized water makes the titanium isopropylate complete hydrolysis obtain white precipitate, separate this white precipitate and with deionized water with its washes clean, then after adding the 30mL deionized water in the precipitation, while stirring to the concentrated nitric acid that wherein slowly drips about 20mL, fully stirring is dissolved precipitation fully, obtains the solution of clear; Add again weight range in the solution and can be controlled in the urea of 0.72g-7.2g and suitable deionized water (in the present embodiment, specifically having added the urea of 4.50g and an amount of deionized water), form the clear mixing solutions of 100ml after the magnetic agitation; Above-mentioned mixing solutions is placed 500 ℃ High Temperature Furnaces Heating Apparatus, and violent combustion reactions occurs, the complete rear acquisition puffy powder of combustion reactions in solution after evaporation, boiling and bubbling.This powder is ground with mortar, obtain the 2# sample.
Fig. 3 is the scanning electron microscope (SEM) photograph according to the embodiment of the invention 2 prepared 2# samples, and as seen from the figure, the size distribution of 2# sample is comparatively even, and particle size is less, and median size is about 25nm.
Take by weighing the tetrabutyl titanate of 10.2g, adding an amount of deionized water makes the tetrabutyl titanate complete hydrolysis obtain white precipitate, separate this white precipitate and with deionized water with its washes clean, then after adding the 30mL deionized water in the precipitation, while stirring to the concentrated nitric acid that wherein slowly drips about 20mL, fully stirring is dissolved precipitation fully, obtains the solution of clear; Add again weight range in the solution and be controlled at glycine in the scope of 1.13g-3.38g and an amount of deionized water (specifically adding in the present embodiment the glycine of 2.50g and an amount of deionized water), form the clear mixing solutions of 100ml after the magnetic agitation; Above-mentioned mixing solutions is placed 600 ℃ High Temperature Furnaces Heating Apparatus, and violent combustion reactions occurs, the complete rear acquisition puffy powder of combustion reactions in solution after evaporation, boiling and bubbling.This powder is ground with mortar, obtain the 3# sample.
Fig. 4 is the scanning electron microscope (SEM) photograph according to the embodiment of the invention 3 prepared 3# samples, and as seen from the figure, the size distribution of 1# sample is comparatively even, and particle size is less, and median size is about 60nm.
Take by weighing the titanium isopropylate of 8.53g, adding an amount of deionized water makes the titanium isopropylate complete hydrolysis obtain white precipitate, separate this white precipitate and with deionized water with its washes clean, then after adding the 30mL deionized water in the precipitation, while stirring to the concentrated nitric acid that wherein slowly drips about 20mL, fully stirring is dissolved precipitation fully, obtains the solution of clear; Add again weight range in the solution and can be controlled in the citric acid of 3.15g-9.46g and an amount of deionized water (specifically having added in the present embodiment the citric acid of 3.78g and an amount of deionized water), form the clear mixing solutions of 100ml after the magnetic agitation; Above-mentioned mixing solutions is placed 600 ℃ High Temperature Furnaces Heating Apparatus, and violent combustion reactions occurs, the complete rear acquisition puffy powder of combustion reactions in solution after evaporation, boiling and bubbling.This powder is ground with mortar, obtain the 4# sample.
Fig. 5 is the scanning electron microscope (SEM) photograph according to the embodiment of the invention 4 prepared 4# samples, and as seen from the figure, the size distribution of 4# sample is comparatively even, and median size is about 150nm.
The below carries out the test of XRD figure spectrum to the above 1#-4# sample that makes.Fig. 6 carries out the XRD figure spectrum that test forms to above 1#-4# sample, from relatively can finding out of the XRD of 1# and 2#, and when urea amount is less, synthetic TiO
2All be Anatase, along with the increase of urea content, occur simultaneously Anatase and Rutile Type in the powder; 3# and 4# sample be respectively take glycine and citric acid as organic-fuel, also can synthesize to have Anatase and Rutile Type rutile TiO
2Powder.
The 1#-4# sample of 200mg is joined respectively in the methyl orange solution of 10mg/L of 100ml, in the dark stir 30min reach the dissolving adsorption equilibrium after, adopting the high voltage mercury lamp of 50W is light source, liquid level and ultraviolet lamp distance is 25cm, and the mode by magnetic agitation and water-bath so that temperature be controlled at about 293K.Shine sampling after five hours, after centrifugation, get isolated settled solution, adopt the UV-2550 ultraviolet spectrophotometer to measure the absorbancy of clear liquor, calculate the degradation efficiency of catalyzer.Fig. 7 adopts methyl orange solution to carry out the degradation rate synoptic diagram of test to above 1#-4# sample, and as shown in Figure 7, the photocatalytic activity of 1# and 2# sample is all higher, and degradation rate is respectively 80.1% and 70.1% methyl orange solution shines 5h under UV-light after.
Those skilled in the art will readily understand; the above only is preferred embodiment of the present invention; not in order to limiting the present invention, all any modifications of doing within the spirit and principles in the present invention, be equal to and replace and improvement etc., all should be included within protection scope of the present invention.
Claims (8)
1. the method for the preparation of the mixing crystal formation titanic oxide nano powder that comprises Detitanium-ore-type and rutile-type is characterized in that the method comprises the following steps:
(a) tetrabutyl titanate or titanium isopropylate are joined form white precipitate in the deionized water, separate this white precipitate and washes clean, and then be distributed in the deionized water, and to drip while stirring concentration be 40% ~ 63% nitric acid, makes transparent titanium salt solution after fully stirring;
(b) add in the prepared titanium salt solution as the urea of reductive agent and fuel forming mixing solutions, and the mol ratio between the titanium ion in this urea and the described titanium salt solution is 0.4-4.0;
(c) place 300 ℃-600 ℃ High Temperature Furnaces Heating Apparatus to carry out self-propagating combustion the formed mixing solutions of step (b), obtain to include simultaneously thus the mixing crystal formation titanic oxide nano powder of Detitanium-ore-type and two kinds of structures of rutile-type.
2. the method for claim 1 is characterized in that, in step (b), the mol ratio between the titanium ion in described urea and the titanium salt solution is 0.45-2.5.
3. method as claimed in claim 1 or 2 is characterized in that, in step (c), when adopting urea to act as a fuel, the ignition temperature of carrying out described self-propagating combustion is about 500 ℃.
4. the method for claim 1 is characterized in that, in step (b), can also for example adopt glycine or citric acid to replace described urea, and the mol ratio between the titanium ion in itself and the titanium salt solution is 0.5-1.5.
5. method as claimed in claim 4 is characterized in that, in step (c), when adopting glycine or citric acid to act as a fuel, the ignition temperature of carrying out described self-propagating combustion is about 600 ℃.
6. such as the described method of claim 1-4 any one, it is characterized in that, in step (b), add in the described titanium salt solution in the process of described fuel and carry out magnetic agitation.
7. such as the prepared mixing crystal formation of the described method of claim 1-6 any one titanic oxide nano powder product.
8. mixing crystal formation titanic oxide nano powder product as claimed in claim 7 is characterized in that the particle diameter mean sizes of described powder-product is about 15nm-150nm.
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Cited By (3)
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| CN104445385A (en) * | 2014-11-21 | 2015-03-25 | 南京大学昆山创新研究院 | TiO2 nano powder, preparation process of TiO2 nano powder by microemulsion combustion method, and application of TiO2 nano powder to preparation of DSSC photo-anode TiO2 slurry |
| CN104030348B (en) * | 2014-05-14 | 2015-08-19 | 浙江大学 | A kind of preparation method of titanium dioxide nano-belts |
| CN108097225A (en) * | 2017-11-23 | 2018-06-01 | 昆明理工大学 | A kind of method that crystal type nano TiO 2 is prepared using seed crystal induction |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104030348B (en) * | 2014-05-14 | 2015-08-19 | 浙江大学 | A kind of preparation method of titanium dioxide nano-belts |
| CN104445385A (en) * | 2014-11-21 | 2015-03-25 | 南京大学昆山创新研究院 | TiO2 nano powder, preparation process of TiO2 nano powder by microemulsion combustion method, and application of TiO2 nano powder to preparation of DSSC photo-anode TiO2 slurry |
| CN108097225A (en) * | 2017-11-23 | 2018-06-01 | 昆明理工大学 | A kind of method that crystal type nano TiO 2 is prepared using seed crystal induction |
| CN108097225B (en) * | 2017-11-23 | 2021-05-14 | 昆明理工大学 | Method for preparing crystal form nano titanium dioxide by seed crystal induction |
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