CN105271400B - A kind of preparation method of mixed crystal nano-titanium dioxide - Google Patents
A kind of preparation method of mixed crystal nano-titanium dioxide Download PDFInfo
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Abstract
The present invention relates to a kind of preparation method of mixed crystal nano-titanium dioxide, the method is by the TiCl of certain volume4It is slowly dissolve into deionized water, after after stabilization, respectively in two temperature section continuous ageing regular hours of low temperature (30~60 DEG C) and high temperature (60~90 DEG C), it is not necessary to any additive, only by controlling TiCl4The content (16.8~75.6%) of solution Rutile Type in low temperature and the length of high temperature ageing time, regulation and control final products.The mixed crystal nano-titanium dioxide powder of rutile/sharp titanium different proportion is obtained after the sediment filtering, washing, the drying that will finally obtain.
Description
Technical field
The present invention relates to field of nanometer material technology, more particularly, to a kind of preparation method of mixed crystal nano-titanium dioxide.
Background technology
In recent years, environment and energy problem caused the highest attention of people.In huge textile industry production process,
Dyestuff is difficult to remove, photocatalytic degradation as organic pollution very serious in ecological environment with the method for biological and physics
Pollutant is considered as always effective method.And nano titanium oxide is used as a kind of nontoxic, cheap and stable in properties nanometer
Material, is expected to turn into most promising photochemical catalyst.
Nano titanium dioxide, also known as titanium dioxide, below 100 nanometers, product appearance is fluffy white powder to diameter.
TiO2Nano particle is stable in properties, and it is good to catch optical property, recoverable.TiO2Application field it is also boundless, be widely used in
The aspect such as energy and environment, biological aspect, medical treatment and health, with following advantage：
1st, photocatalytic pollutant degradation：Nano-TiO2As catalyst, there is no secondary pollution and without selectivity, extensively should
For environmental pollution aspect.Can be with degradation of dye waste water, insecticide, agricultural chemicals waste water, also surfactant, the work containing heavy metal
Industry waste water, can be oxidized degraded；
2nd, the application in terms of DSSC：Semiconductor nano TiO2There is broader energy gap, and very
Good light fastness.Dyestuff photosensitive molecular is adsorbed in semiconductor nano TiO2Surface improve photoelectric transformation efficiency；
3rd, nano-TiO2Shielding action to ultraviolet：Nano-TiO2There is certain shielding action to ultraviolet, along with it
Nontoxic, stable in properties the features such as, make nano-TiO2It is applied to the sun-proof of cosmetics, coating, chemical fibre, rubber, plastics etc. each
Individual aspect.
Nano titanium oxide mainly has two kinds of crystal habits：Anatase titanium dioxide (Anatase) and rutile-type (Rutile).Golden red
Stone-type titanium dioxide is finer and close than anatase titanium dioxide stabilization, there is hardness higher, density, dielectric constant and refractive index, its
Covering power and tinting strength, tinting power are also higher.And anatase titanium dioxide is in the luminance factor rutile-type titanium dioxide of visible ray shortwave part
Titanium is high, band blue color, and lower than rutile-type to the absorbability of ultraviolet, and photocatalytic activity is higher than rutile-type.
Under certain condition, anatase titanium dioxide can be converted into rutile titanium dioxide.
In the existing preparation process of mixed crystal nano-titanium dioxide, in order to prepare qualified nanometer titanium dioxide titanium products,
Precipitating reagent is often added in preparation process and is heat-treated, such as：(Wang Wei, Ruan Chengdong, Ru Hongqiang are a kind of mesoporous for Wang Weis etc.
Titanium dioxide color material and preparation method thereof, China, patent of invention, 201410231843.2,2014.08.13) use titanium source (tetrachloro
Change titanium, titanium trichloride, one or two in titanate esters) metatitanic acid is prepared with water reaction, metatitanic acid and hydrogen peroxide are mixed with
Go out peroxidating metatitanic acid, nonionic surface active agent and peroxidating metatitanic acid are formed into composite, and composite is roasted
Burning obtains mesoporous TiO 2.(Wang Bing, Yang Zewei, An Hao wait a kind of brockites of and rutile titanium dioxide nanometer to Wang Bing etc.
The low temperature preparation method China of mixed crystal, patent of invention, 201410629923.3,2015.03.25) by ultra-pure water, metatitanic acid tetrem
Ester and absolute ethyl alcohol are mixed with and hydrous titanium oxide are obtained after drying by a certain percentage, plus the prepared pertitanic acid of hydrogen peroxide is molten
Glue, by colloidal sol water-bath at 40~60 DEG C, finally carries out hydro-thermal reaction, the scrubbed drying of product under conditions of 160~200 DEG C
Obtain mixed crystal afterwards.(the synthesis of Wang Zhenxing, Ding Shiwen, Zhang Meihong high-dispersion nano titanium dioxide mixed crystals such as Wang Zhenxing！
Structure and photocatalysis performance, Chinese Journal of Inorganic Chemistry, 2005,3,21) titanium tetrachloride is measured slowly with drying graduated cylinder in fume hood
It is added in hydrochloric acid solution.Mixed solution is heated rapidly to again will be dissolved with a certain amount of urine after 100 DEG C of 10~60min of isothermal reaction
The aqueous solution of element is rapidly joined in solution.In the basic conditions in 100 DEG C of back flow reaction 2h decompressions suction filtrations, washings.Then dry,
It is finally putting into Muffle furnace calcination 30min and takes out sample.There is hard aggregation in drying course to prevent nano-particle, in mixing
A certain amount of nanoscale carbon black is added in solution.(Ding Shiwen, Dong Wei, Wang Liyong wait mixed crystal nano-TiOs to Ding Shiwen etc.2System
It is standby and to the Study on degradation of cyanide wastewater, University Of Xiangtan's natural science journal, 2008,2,30.) 11mL TiCl are slowly added dropwise
To in 200mL distilled water, drop speed 1d/s is kept, solution clarification is kept in titration process.Settled solution in beaker is gone to
In 500mL three-necked bottles, boiling is heated in acid condition, continue to react 10~60min, Ran Houjia after muddiness occurs in solution
The ammoniacal liquor for entering 1ml adjusts pH value to alkalescent, continues to react 60min.Decompression suction filtration, washing, powder is dried to obtain at 80~90 DEG C
Roasting 60min in people's muffle furnace is put after last sample.Wang Li bravely waits (the mixed crystal nanometer titanium dioxides such as Wang Liyong, Bai Zhenyu, Dong Wei
The synthesis of titanium is studied with light degradation acid red 3R, University Of Hebei's journal (natural science edition), 2007,3,27) by TiCl4With per second
1 drop speed is instilled in 200mL deionized waters, is rapidly heated, and a large amount of white casses occurs to system, when reacting one section for 100 DEG C
Between after, volume fraction is that 50% ammoniacal liquor is neutralized to alkalescent, and after continuing to react 3h at 100 DEG C, product is through filtering, deionized water
Wash away NH4+And Cl-Foreign ion, then the moisture remained in sample is washed away with absolute ethyl alcohol, vacuum drying, finely ground, prepared nanometer
Mixed crystal powder.Season, gold careless waited that (season, gold was careless, and Guo Jing, Shi Chaohui wait preparation and its light of mixed crystal form nanometer titanium dioxide turbid liquors
Catalytic performance material Leaders B：A research piece, 2012,7,26) drip TiCl in the mixed solution of ammoniacal liquor and water4Solution, high temperature oil
Bath heating, pH value is adjusted with concentrated hydrochloric acid, can obtain white precipitate TiO2.(Du Jinge, Yao is towards ancestor's nano titanium oxides for Du Jinge etc.
Preparation and its photocatalysis performance, chemical research, 2012,4,23) titanium tetrachloride is added to distilled water and ethanol mixing it is molten
In liquid, stirring is slowly added dropwise urea liquid, after room temperature at the uniform velocity stirs 2h, is transferred to the autoclave of polytetrafluoroethyllining lining
In, 180 DEG C of constant temperature treatment 16h in air dry oven.Room temperature is cooled to, filtering, washing, 60 DEG C of drying obtain TiO2Receive
Ground rice body.In the preparation process of mixed crystal nano-titanium dioxide, bronsted lowry acids and bases bronsted lowry is participated in preparation process, follow-up heat as precipitating reagent
Processing procedure also increases the complexity of preparation process.The present invention by the control to reaction temperature and reaction time without
Precipitating reagent and the controllable mixed crystal nano silicon of crystal form ratio is prepared in the case of carrying out subsequent heat treatment, reduce preparation
The complexity of process.
The content of the invention
In view of the above problems, the invention provides a kind of preparation method of mixed crystal nano-titanium dioxide, can once make
The titanium dioxide of anatase titanium dioxide and rutile-type mixing crystal formation is obtained during standby simultaneously.Concrete technical scheme is as follows：
A kind of preparation method of mixed crystal nano-titanium dioxide, it is characterised in that comprise the following steps：
First, by TiCl4It is dissolved in deionized water, is configured to certain density TiCl4The aqueous solution；Then, 30~60
Aging 2~8h and/or aging 2~8h at a high temperature of 60~90 DEG C in a low temperature of DEG C, will obtain sediment filtering, washing,
Dry, in the process, it is not necessary to add any reagent and regulation pH value；Finally, the mixed crystal nano-titanium dioxide is obtained；
The TiCl4It is 1 with the volume ratio of deionized water：100~1：30.
The mixed crystal refers to the two kinds of mixing of crystal formation of anatase titanium dioxide and rutile-type.
The weight of the anatase titanium dioxide and rutile-type is than 10~80：20~90.
Present inventor it has been investigated that, be probably the life at different temperatures of two kinds of crystal formations the reason for mixed crystal is generated
It is different into speed：During low temperature, it is very fast that rutile-type grows；During high temperature, it is very fast that anatase titanium dioxide grows.So being given birth in low temperature
Into mixed crystal in rutile content it is high, anatase content is high after high―temperature nuclei.In order to adjust the ratio of mixed crystal, using in low high temperature
Two temperature sections, different growth time reaches the purpose of regulation mixed crystal ratio.
The advantages of the present invention are as follows：Nano-titanium oxide is a kind of excellent catalysis material, is particularly had
There is a certain proportion of mixed crystal titanium oxide, traditional method is by changing calcining heat and calcination time or by addition one
The method of a little chemical additives regulates and controls the ratio of mixed crystal, and calcining easily causes sintering and the reunion of particle, adds the side of controlling agent
Method operating process is complicated；And the preparation method that the present invention is provided, it is only necessary to by TiCl4It is dissolved into water, is made into a certain proportion of
The aqueous solution, at different temperature aging different time, it is possible to regulate and control the ratio of sharp titanium and rutile in product.The method
Preparation process is simple, the slurry for obtaining directly can be carried on carrier, it is to avoid the reunion in calcination process.
Brief description of the drawings
Fig. 1 is the X ray diffracting spectrum of the mixed crystal titanium dioxide of embodiment 1；
Fig. 2 is the X-ray diffraction fitting collection of illustrative plates of the mixed crystal titanium dioxide of embodiment 1；
Fig. 3 is the X ray diffracting spectrum of the mixed crystal titanium dioxide of embodiment 2；
Fig. 4 is the X-ray diffraction fitting collection of illustrative plates of the mixed crystal titanium dioxide of embodiment 2；
Fig. 5 is the X ray diffracting spectrum of the mixed crystal titanium dioxide of embodiment 3；
Fig. 6 is the X-ray diffraction fitting collection of illustrative plates of the mixed crystal titanium dioxide of embodiment 3；
Fig. 7 is the X ray diffracting spectrum of the mixed crystal titanium dioxide of embodiment 4；
Fig. 8 is the X-ray diffraction fitting collection of illustrative plates of the mixed crystal titanium dioxide of embodiment 4；
Fig. 9 is the X ray diffracting spectrum of the mixed crystal titanium dioxide of embodiment 5；
Figure 10 is the X-ray diffraction fitting collection of illustrative plates of the mixed crystal titanium dioxide of embodiment 5；
Figure 11 is the X ray diffracting spectrum of the mixed crystal titanium dioxide of embodiment 6；
Figure 12 is the X-ray diffraction fitting collection of illustrative plates of the mixed crystal titanium dioxide of embodiment 6.
Specific embodiment
The present invention is specifically described below by embodiment.Be necessary it is pointed out here that be that following examples are served only for
The invention will be further described, it is impossible to is interpreted as limiting the scope of the invention, professional and technical personnel in the field's root
Some the nonessential modifications and adaptations made according to present disclosure, still fall within protection scope of the present invention.
Embodiment 1
By the TiCl of 3.5mL4It is dissolved in 100mL deionized waters.Solution is put into 45 DEG C of water bath with thermostatic control and heats 6h.
Then gained slurry filtered, is washed, being dried, being obtained mixed crystal titanium oxide powder.Diffracting spectrum that products obtained therefrom is measured and
Fitting collection of illustrative plates difference is as depicted in figs. 1 and 2.Correlation computations data are as follows：
It is 24.4% to be calculated the content of sharp titanium phase in titanium dioxide sample, and average grain diameter is 1.10nm.Rutile Type
Content be 75.6%, average grain diameter be less than 1nm.
Embodiment 2
By the TiCl of 2.5mL4It is dissolved in 100mL deionized waters.Solution is put into 35 DEG C of water bath with thermostatic control and heats 2h,
Solution is put into 85 DEG C of water bath with thermostatic control again after taking-up and heats 6h.Then gained slurry filtered, is washed, being dried, being obtained
To mixed crystal titanium oxide powder.Diffracting spectrum and be fitted collection of illustrative plates difference as shown in Figure 3 and Figure 4 that products obtained therefrom is measured.Correlation computations
Data are as follows：
It is 72.3% to be calculated the content of sharp titanium phase in titanium dioxide sample, and average grain diameter is less than 1nm.Rutile Type
Content is 27.7%, and average grain diameter is 1.06nm.
Embodiment 3
By the TiCl of 2mL4It is dissolved in 100mL deionized waters.Solution is put into 55 DEG C of water bath with thermostatic control and heats 4h, taken
Solution is put into 80 DEG C of water bath with thermostatic control again after going out and heats 4h.Then gained slurry filtered, is washed, being dried, being obtained
Mixed crystal titanium oxide powder.Diffracting spectrum and be fitted collection of illustrative plates difference as shown in Figure 5 and Figure 6 that products obtained therefrom is measured.Correlometer counts
According to as follows：
It is 66.7% to be calculated the content of sharp titanium phase in titanium dioxide sample, and average grain diameter is less than 1nm.Rutile Type
Content is 33.3%, and average grain diameter is 1.34nm.
Embodiment 4
By the TiCl of 3.5mL4It is dissolved in 100mL deionized waters.Solution is put into 80 DEG C of water bath with thermostatic control and heats 8h.
Then gained slurry filtered, is washed, being dried, being obtained mixed crystal powder.Diffracting spectrum and fitted figure that products obtained therefrom is measured
Spectrum difference is as shown in Figure 7 and Figure 8.Correlation computations data are as follows：
It is 83.2% to be calculated the content of sharp titanium phase in titanium dioxide sample, and average grain diameter is less than 1nm.Rutile Type
Content is 16.8%, and average grain diameter is 1.51nm.
Embodiment 5
By the TiCl of 3mL4It is dissolved in 100mL deionized waters.Solution is put into 70 DEG C of water bath with thermostatic control and heats 2h, taken
Solution is put into 45 DEG C of water bath with thermostatic control again after going out and heats 6h.Then gained slurry filtered, is washed, being dried, being obtained
Mixed crystal titanium oxide powder.Diffracting spectrum and be fitted collection of illustrative plates difference as shown in Figure 9 and Figure 10 that products obtained therefrom is measured.Correlometer counts
According to as follows：
It is 78.7% to be calculated the content of sharp titanium phase in titanium dioxide sample, and average grain diameter is less than 1nm.Rutile Type
Content is 21.3%, and average grain diameter is less than 1nm.
Embodiment 6
By the TiCl of 1.5mL4It is dissolved in 100mL deionized waters.Solution is put into aging 4h in 80 DEG C of water bath with thermostatic control,
Solution is put into aging 4h in 45 DEG C of water bath with thermostatic control again after taking-up.Then gained slurry filtered, is washed, being dried, being obtained
To mixed crystal titanium oxide powder.Diffracting spectrum and be fitted collection of illustrative plates difference as is illustrated by figs. 11 and 12 that products obtained therefrom is measured.Correlometer
Count according to as follows：
It is 80% to be calculated the content of sharp titanium phase in titanium dioxide sample, and average grain diameter is less than 1nm.Rutile Type contains
It is 20% to measure, and average grain diameter is 1.42nm.
Claims (4)
1. a kind of preparation method of mixed crystal nano-titanium dioxide, it is characterised in that comprise the following steps：
First, by TiCl4It is dissolved in deionized water, is configured to certain density TiCl4The aqueous solution；Then, at 30~60 DEG C
Aging 2~8h and/or aging 2~8h at a high temperature of 60~90 DEG C under low temperature, the sediment that will be obtained is filtered, washs, dried,
Finally, the mixed crystal nano-titanium dioxide is obtained；
The TiCl4It is 1 with the volume ratio of deionized water：100~1：30.
2. preparation method according to claim 1, it is characterised in that the mixed crystal refers to two kinds of anatase titanium dioxide and rutile-type
The mixing of crystal formation.
3. preparation method according to claim 2, it is characterised in that the weight of the anatase titanium dioxide and rutile-type than 10~
80：20~90.
4. the preparation method of mixed crystal nano-titanium dioxide according to claim 1, it is characterised in that TiCl4The aqueous solution is aging
In 60~90 DEG C of stages of 30~60 DEG C of stages of low temperature and high temperature of process, may be used alone, can also be used in combination, total is aging
Time is 4~8h.
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| CN112645382B (en) * | 2019-10-09 | 2023-05-30 | 万华化学集团股份有限公司 | Preparation method of nano titanium dioxide, nano titanium dioxide and application |
| CN111634943B (en) * | 2020-06-15 | 2022-08-23 | 上海工程技术大学 | Crystalline phase regulation and control method of titanium dioxide nano material |
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| CN101306838B (en) * | 2008-07-01 | 2010-09-22 | 上海大学 | Method for preparing high- stable neutral mixed crystal nanometer TiO2 hydrosol |
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