CN107253736B - A kind of preparation method of anatase titanium dioxide monocrystalline - Google Patents
A kind of preparation method of anatase titanium dioxide monocrystalline 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 94
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 44
- 239000004408 titanium dioxide Substances 0.000 claims abstract description 26
- 239000004530 micro-emulsion Substances 0.000 claims abstract description 21
- ZSIAUFGUXNUGDI-UHFFFAOYSA-N hexan-1-ol Chemical compound CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 claims abstract description 20
- 238000000034 method Methods 0.000 claims abstract description 14
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 11
- 239000010936 titanium Substances 0.000 claims abstract description 11
- GPRLSGONYQIRFK-MNYXATJNSA-N triton Chemical compound [3H+] GPRLSGONYQIRFK-MNYXATJNSA-N 0.000 claims abstract description 11
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000004202 carbamide Substances 0.000 claims abstract description 9
- NMGYKLMMQCTUGI-UHFFFAOYSA-J diazanium;titanium(4+);hexafluoride Chemical compound [NH4+].[NH4+].[F-].[F-].[F-].[F-].[F-].[F-].[Ti+4] NMGYKLMMQCTUGI-UHFFFAOYSA-J 0.000 claims abstract description 9
- 239000003153 chemical reaction reagent Substances 0.000 claims abstract description 7
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 claims abstract description 7
- 230000001376 precipitating effect Effects 0.000 claims abstract description 7
- 239000013049 sediment Substances 0.000 claims description 13
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 9
- 238000006243 chemical reaction Methods 0.000 claims description 8
- 239000008367 deionised water Substances 0.000 claims description 7
- 229910021641 deionized water Inorganic materials 0.000 claims description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- 229960000935 dehydrated alcohol Drugs 0.000 claims description 5
- 238000000227 grinding Methods 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 4
- 239000007864 aqueous solution Substances 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 3
- 150000001875 compounds Chemical class 0.000 claims description 2
- 230000001699 photocatalysis Effects 0.000 abstract description 12
- 239000002245 particle Substances 0.000 abstract description 10
- 238000009826 distribution Methods 0.000 abstract description 7
- 239000000203 mixture Substances 0.000 abstract description 7
- 230000000694 effects Effects 0.000 abstract description 5
- 239000006185 dispersion Substances 0.000 abstract description 2
- 239000003054 catalyst Substances 0.000 description 11
- 238000013019 agitation Methods 0.000 description 8
- 238000004090 dissolution Methods 0.000 description 6
- 239000007788 liquid Substances 0.000 description 6
- 230000035484 reaction time Effects 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 238000007146 photocatalysis Methods 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 230000015556 catabolic process Effects 0.000 description 3
- 238000006731 degradation reaction Methods 0.000 description 3
- 238000011049 filling Methods 0.000 description 3
- 239000000706 filtrate Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 239000006228 supernatant Substances 0.000 description 3
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 3
- 229910052724 xenon Inorganic materials 0.000 description 3
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 3
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 231100001261 hazardous Toxicity 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- STZCRXQWRGQSJD-GEEYTBSJSA-M methyl orange Chemical compound [Na+].C1=CC(N(C)C)=CC=C1\N=N\C1=CC=C(S([O-])(=O)=O)C=C1 STZCRXQWRGQSJD-GEEYTBSJSA-M 0.000 description 2
- 229940012189 methyl orange Drugs 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000000523 sample Substances 0.000 description 2
- STZCRXQWRGQSJD-UHFFFAOYSA-M sodium;4-[[4-(dimethylamino)phenyl]diazenyl]benzenesulfonate Chemical compound [Na+].C1=CC(N(C)C)=CC=C1N=NC1=CC=C(S([O-])(=O)=O)C=C1 STZCRXQWRGQSJD-UHFFFAOYSA-M 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- QNRATNLHPGXHMA-XZHTYLCXSA-N (r)-(6-ethoxyquinolin-4-yl)-[(2s,4s,5r)-5-ethyl-1-azabicyclo[2.2.2]octan-2-yl]methanol;hydrochloride Chemical compound Cl.C([C@H]([C@H](C1)CC)C2)CN1[C@@H]2[C@H](O)C1=CC=NC2=CC=C(OCC)C=C21 QNRATNLHPGXHMA-XZHTYLCXSA-N 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000012496 blank sample Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 239000004064 cosurfactant Substances 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 239000006210 lotion Substances 0.000 description 1
- 238000003760 magnetic stirring Methods 0.000 description 1
- 239000002159 nanocrystal Substances 0.000 description 1
- 239000013642 negative control Substances 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 239000013641 positive control Substances 0.000 description 1
- 239000012488 sample solution Substances 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000000870 ultraviolet spectroscopy Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G23/00—Compounds of titanium
- C01G23/04—Oxides; Hydroxides
- C01G23/047—Titanium dioxide
- C01G23/053—Producing by wet processes, e.g. hydrolysing titanium salts
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
- B01J21/063—Titanium; Oxides or hydroxides thereof
-
- B01J35/39—
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
Abstract
The invention discloses a kind of preparation methods of anatase titanium dioxide monocrystalline.This method is using ammonium titanium fluoride as titanium source, using urea as precipitating reagent, in triton x-100/n-hexyl alcohol/hexamethylene/water composition Reverse Microemulsion System, prepares anatase titanium dioxide monocrystalline using solvent-thermal process method.The microjet that the present invention is generated by the cavitation effect using ultrasonic wave is mixed evenly oily phase and water phase, to control partial size and distribution of the water phase in oily phase, avoids the reunion of titanium dioxide single crystalline particle.The particle diameter distribution of anatase titanium dioxide monocrystalline prepared by the present invention is uniform, good dispersion, reunion mild degree, purity is high, and free from admixture has preferable photocatalytic activity.
Description
Technical field
The present invention relates to photochemical catalyst field more particularly to a kind of preparation methods of anatase titanium dioxide monocrystalline.
Background technique
TiO2Since with high photocatalytic activity, fast light corrosive power is strong, environmental-friendly, relative low price and to people
A kind of the advantages that body is non-toxic, it has also become semiconductor material that people are most interested in photocatalytic pollutant degradation field.TiO2
There are three types of crystalline structures: Detitanium-ore-type, rutile-type and brookite type.Brookite type category rhombic system, photocatalytic activity is low, is
A kind of metastable state, research is seldom at present.Around Detitanium-ore-type and rutile TiO2A large amount of research is done.Rutile TiO2
Heat resistance, thermal stability, chemical stability are superior to Detitanium-ore-type TiO2, can be widely applied to coating, paint, cosmetics, modeling
The fields such as material；And when being used as catalysis material, Detitanium-ore-type TiO2Photocatalytic activity is then apparently higher than rutile TiO2, in environment
The fields such as improvement, organic synthesis, photocatalytic water show wide application prospect.
2008,2008,453 (29): Yang etc. is reported in 638 with the lower TiF of hydrolysis rate in nature4For
Titanium source, using hydro-thermal method, has synthesized micron order Detitanium-ore-type TiO using HF as pattern controlling agent2Monocrystalline.2009, Han existed
The Anatase TiO that J.AM.CHEM.SOC.2009,131,3152-3153 etc. is reported2Nano crystal.But in the studies above
In, researcher all employs HF (hydrofluoric acid) to obtain TiO2Monocrystalline.And HF is a kind of liquid with aggressive, directly
It is relatively hazardous using HF, there is the problems such as corrosion equipment and pollution environment.
Summary of the invention
In view of the above shortcomings of the prior art, the purpose of the present invention is to provide a kind of anatase titanium dioxide lists
Brilliant preparation method, avoids the liquid HF using aggressive, solves the problems such as equipment corrosion and environmental pollution.
To achieve the above object, the present invention adopts the following technical scheme: a kind of preparation of anatase titanium dioxide monocrystalline
Method, which comprises the steps of:
1) water phase is prepared
Compound concentration is the aqueous solution of the titanium source of 300g/L, then weighs precipitating reagent in proportion and is added to titanium source aqueous solution
In, magnetic stirrer stirs 1~3h, obtains water phase, and the molar ratio of the titanium source and precipitating reagent is 1:3~10；
2) oily phase is prepared
Triton x-100, n-hexyl alcohol and hexamethylene are measured respectively, and are added sequentially in beaker, magnetic stirrer 1
~3h, obtains oily phase, and the triton x-100, n-hexyl alcohol and cyclohexane volume ratio are 1.2~2:0.7~1.2:2.1~2.8；
3) microemulsion is prepared
The oily phase that step 2) obtains is measured, is added in beaker, and place the beaker in ultrasonic field, ultrasonic power 100
~300W, ultrasonic time are 0.5~3h, then measure the water phase that step 1) obtains, and water phase is dripped with the speed of 1~3mL/min
It is added in oily phase, after being added dropwise, stops after continuing 0.5~1h of ultrasonic disperse, obtain microemulsion, the oil phase and water phase volume
Than for 15~2:1；
4) solvent-thermal process method prepares anatase titanium dioxide monocrystalline
The microemulsion that step 3) is obtained is transferred in hydrothermal reaction kettle, and reaction kettle is placed in 120~200 DEG C of drying
It in case, after reacting 8~16h, is cooled to room temperature, then filters, collect sediment；By sediment successively with dehydrated alcohol and go from
Sub- water washing is to neutrality, and in 60 DEG C of dry 12h, grinding is finally placed in 450~550 DEG C of Muffle 1~3h of kiln roasting, obtains rutile titania
Mine type titanium dioxide single crystalline.
Further, titanium source described in step 1) is ammonium titanium fluoride, and the precipitating reagent is urea, and ammonium titanium fluoride rubs with urea
You are than being 1:4~8.
Further, triton x-100 described in step 1), n-hexyl alcohol and cyclohexane volume ratio are 1.5:1:2.5.
Further, oil described in step 3) is mutually 13~5:1 with water phase volume ratio.
Further, ultrasonic power described in step 3) is 200~300W, and ultrasonic time is 0.5~1h.
Further, the reaction temperature of drying box described in step 4) is 150~180 DEG C, 12~14h of reaction time.
Compared with prior art, the invention has the following beneficial effects:
1, in preparation process of the present invention, using ammonium titanium fluoride as titanium source, using urea as precipitating reagent, triton x-100/just oneself
In alcohol/hexamethylene/water composition Reverse Microemulsion System, anatase titanium dioxide monocrystalline is prepared using solvent-thermal process method,
It avoids using HF, safety and environmental protection, it is non-hazardous to human body and environment.With easy to operate.
2, the present invention prepares titanium dioxide single crystalline using ultrasound-microemulsion-solvent-thermal process method.Microemulsion be by it is oily mutually and
Thermodynamically stable system made of water phase stirring.Wherein, oil is mutually by surfactant, cosurfactant and continuous phase group
At water phase is by titanium source and the material composition for having other assisted reactions.In the microemulsion of water-in-oil type, surfactant and table is helped
The hydrophilic radical and water of face activating agent combine, and lipophilic group and oil combine, and such water phase is formed " reaction in oily phase
Device " promotes to form and numerous small has been even up to micron or nanoscale " microreactor " by agitation.Pass through utilization
The microjet that the cavitation effect of ultrasonic wave generates, big " microreactor " is smashed, and is mixed evenly oily phase and water phase, to control
" microreactor " partial size and distribution are made, and then keeps titanium dioxide single crystalline grain diameter obtained uniform.
3, the present invention further by regulation oil mutually with the volume ratio of water phase, the rate of addition of water phase, ultrasonic power, react
The optimization of temperature and reaction time, to control TiO2Single crystal grain size distribution situation and reunion degree.Prepared by the present invention two
Titanium oxide monocrystalline partial size is evenly distributed, good dispersion, almost without the reunion of particle, has preferable photocatalytic activity.
Detailed description of the invention
Fig. 1 is the SEM phenogram of the titanium dioxide single crystalline prepared in embodiment 1；
Fig. 2 is the SEM phenogram of the titanium dioxide single crystalline prepared in embodiment 2；
Fig. 3 is the SEM phenogram of the titanium dioxide single crystalline prepared in embodiment 3；
Fig. 4 is the titanium dioxide single crystalline XRD detection figure prepared in embodiment 1-3；
Fig. 5 is the effect contrast figure that xenon lamp irradiates lower different catalysts photo-catalytic degradation of methyl-orange (20mg/L).
Specific embodiment
Invention is further described in detail with attached drawing combined with specific embodiments below.
One, a kind of preparation method of anatase titanium dioxide monocrystalline
Embodiment 1:
1) it weighs 1.5g ammonium titanium fluoride to be added in the beaker for filling 5mL deionized water, stirs to whole dissolutions, add
1.8g urea is stirred to whole dissolutions, as microemulsion water phase.
2) 12mL triton x-100,8mL n-hexyl alcohol and 20mL hexamethylene are measured, is added sequentially in the beaker of 250mL,
1~3h of magnetic agitation, until solution presentation is transparent uniform, as microemulsion oil phase.
3) the oily phase for obtaining step 2), is placed in ultrasonic field, ultrasonic power 300W, then by water phase with 1mL/min
Speed be evenly added drop-wise in the oily phase being stirred continuously, after being added dropwise, continue ultrasonic disperse 1h, formed it is translucent uniform
Microemulsion.
4) microemulsion is moved into the autoclave with polytetrafluoroethyllining lining, the compactedness of hydrothermal reaction kettle is
80%, at 180 DEG C, reaction time 12h is then cooled to room temperature.
5) supernatant liquor in hydrothermal reaction kettle is removed, remaining solid-liquid mixture is filtered, collect sediment；
6) sediment that step 5) obtains successively is washed several times with dehydrated alcohol and deionized water, in filtrate is in
Property；
7) sediment after step 6) washing is dried into 12h at 60 DEG C；
8) after the product grinding obtained step 7), it is put into 500 DEG C of Muffle kiln roasting 2h, 1# titanium dioxide list is made
It is brilliant.
Embodiment 2
1) it weighs 1.5g ammonium titanium fluoride to be added in the beaker for filling 5mL deionized water, stirs to whole dissolutions, add
1.8g urea is stirred to whole dissolutions, as microemulsion water phase.
2) 12mL triton x-100,8mL n-hexyl alcohol and 20mL hexamethylene are measured, is added sequentially in the beaker of 250mL,
1~3h of magnetic agitation, until solution presentation is transparent uniform, as microemulsion oil phase.
3) the oily phase for obtaining step 2), is placed in ultrasonic field, ultrasonic power 300W, by water phase with the speed of 3mL/min
Degree is evenly added drop-wise in the oily phase being stirred continuously, and after being added dropwise, continues ultrasonic disperse 1h, is formed translucent uniform micro-
Lotion.
4) microemulsion is moved into the autoclave with polytetrafluoroethyllining lining, the compactedness of hydrothermal reaction kettle is
80%, at 180 DEG C, reaction time 12h is then cooled to room temperature.
5) supernatant liquor in hydrothermal reaction kettle is removed, remaining solid-liquid mixture is filtered, collect sediment；
6) sediment that step 5) obtains successively is washed several times with dehydrated alcohol and deionized water, in filtrate is in
Property；
7) sediment after step 6) washing is dried into 12h at 60 DEG C；
8) after the product grinding obtained step 7), it is put into 500 DEG C of Muffle kiln roasting 2h, 2# titanium dioxide list is made
It is brilliant.
Embodiment 3
1) it weighs 1.5g ammonium titanium fluoride to be added in the beaker for filling 5mL deionized water, stirs to whole dissolutions, add
1.8g urea is stirred to whole dissolutions, as microemulsion water phase.
2) 12mL triton x-100,8mL n-hexyl alcohol and 20mL hexamethylene are measured, is added sequentially in the beaker of 250mL,
1~3h of magnetic agitation, until solution presentation is transparent uniform, as microemulsion oil phase.
3) the oily phase for obtaining step 2), is placed on magnetic stirring apparatus, and water phase is evenly added dropwise with the speed of 1mL/min
Into the oily phase being stirred continuously, after being added dropwise to complete, continues magnetic agitation 1h, form translucent uniform microemulsion.
4) microemulsion is moved into the autoclave with polytetrafluoroethyllining lining, the compactedness of hydrothermal reaction kettle is
80%, at 180 DEG C, reaction time 12h is then cooled to room temperature.
5) supernatant liquor in hydrothermal reaction kettle is removed, remaining solid-liquid mixture is filtered, collect sediment；
6) sediment that step 5) obtains successively is washed several times with dehydrated alcohol and deionized water, in filtrate is in
Property；
7) sediment after step 6) washing is dried into 12h at 60 DEG C；
8) after the product grinding obtained step 7), it is put into 500 DEG C of Muffle kiln roasting 2h, 3# titanium dioxide list is made
It is brilliant.
Two, the characterization and test of titanium dioxide single crystalline
1, the titanium dioxide single crystalline prepared in Examples 1 to 3 is subjected to SEM characterization respectively, obtains Fig. 1~3.
It will be seen from figure 1 that 1# titanium dioxide single crystalline particle is substantially in that octahedron is spherical, and particle size distribution is more uniform,
And degree of reuniting is small；Figure it is seen that 2# titanium dioxide single crystalline particle size distribution is uneven, reunion degree is small；From figure
Although 3 as can be seen that the reunion degree of 3# titanium dioxide single crystalline particle is more serious.
After being mixed due to water phase and oil, water phase is formed " reactor " in oily phase, after magnetic stirrer, and
Oily phase and water phase cannot be made to be mixed evenly, keep the reunion degree of titanium dioxide single crystalline particle obtained more serious；But pass through utilization
The microjet that the cavitation effect of ultrasonic wave generates promotes to form and numerous small has been even up to micron first by agitation
Or nanoscale " microreactor ".And then microjet smashes big " microreactor ", is mixed evenly oily phase and water phase, makes to make
The titanium dioxide single crystalline particle agglomeration degree obtained is small, and needs to control oily phase rate of addition, to control " micro- reaction
Device " partial size and distribution keep titanium dioxide single crystalline grain diameter obtained uniform.As can be seen that rate of addition is 1mL/min when system
The titanium dioxide single crystalline grain diameter obtained is substantially better than 3mL/min.
2, it using the D2PHASER type X-ray diffractometer measurement of German Brooker company manufacture prepared by Examples 1 to 3
Titanium dioxide single crystalline carries out XRD test respectively.
Test condition are as follows: Cu target radiographic source (λ=0.154056nm), power are 30kV × 10mA, and measurement temperature is 25 DEG C,
Stride is 0.02s, residence time 0.2s, and 2 θ angular regions of scanning are 10 °~80 °, obtains Fig. 4.
From fig. 4, it can be seen that the diffraction maximum position (2 θ) of 1#, 2# and 3# titanium dioxide single crystalline with JCPDS No.21-
1272 anatase titania is consistent, and does not detect other substances, illustrates titanium dioxide single crystalline made from this method
For Detitanium-ore-type, and purity is high, free from admixture.
3, limited in Beijing NewBide science and technology with the photocatalysis performance evaluation of the titanium dioxide single crystalline of Examples 1 to 3 preparation
The Phchem type III photochemical reactor of company's production carries out.The photocatalysis performance of sample is commented by degradation methyl orange solution
Valence.As a comparison, Degussa P25 is positive control as catalyst, and it is negative control, control group light degradation that catalyst, which is not added,
Methyl orange experiment also carries out under the conditions of same light is shone.Light source is the visible light of 350W xenon lamp.Obtained two in Examples 1 to 3
Oxidation ti single crystal is 1#, 2# and 3# catalyst.
The methyl orange solution 50mL that concentration is 20mg/L is taken to add in the photocatalysis container of 6 Duplicate Samples, then respectively respectively
Enter 0.05g 1# catalyst, 2# catalyst, 3# catalyst and Degussa P25, catalyst is not added in blank sample.It again will be above-mentioned molten
Liquid is respectively put into reaction camera bellows, and magnetic agitation 1h is to reach adsorption equilibrium, then in the irradiation of 350W xenon lamp (XE-JY500)
Lower progress photocatalysis test.A sample (each 4mL) is taken every 10min, until reaction 120min stops.The sample solution of taking-up passes through
Centrifuge is in 4000rpm, after being centrifugated 15min, then with ultraviolet-visible spectrophotometer in wavelength is that first is tested 462nm at
The concentration of base orange solution changes.
From fig. 5, it is seen that 1# and 2# catalyst obtained has highest photocatalytic activity, it is higher than Degussa
P25.When 3# catalyst is because being added dropwise to oily phase for water phase, using magnetic agitation, mix oily phase and water phase uneven, finally
The reunion degree of titanium dioxide single crystalline particle obtained is more serious, and photocatalytic activity is lower than Degussa P25.
The above embodiment of the present invention is only example to illustrate the invention, and is not to implementation of the invention
The restriction of mode.For those of ordinary skill in the art, other can also be made not on the basis of the above description
With the variation and variation of form.Here all embodiments can not be exhaustive.It is all to belong to technical solution of the present invention
Changes and variations that derived from are still in the scope of protection of the present invention.
Claims (4)
1. a kind of preparation method of anatase titanium dioxide monocrystalline, which comprises the steps of:
1) water phase is prepared
Compound concentration is the aqueous solution of the titanium source of 300 g/L, then weighs precipitating reagent in proportion and is added in titanium source aqueous solution, magnetic
Power blender stirs 1 ~ 3 h, obtains water phase；
The titanium source is ammonium titanium fluoride, and the precipitating reagent is urea, and ammonium titanium fluoride and urea mol ratio are 1:4 ~ 8；
2) oily phase is prepared
Triton x-100, n-hexyl alcohol and hexamethylene are measured respectively, and are added sequentially in beaker, magnetic stirrer 1 ~ 3
H, obtains oily phase, and the triton x-100, n-hexyl alcohol and cyclohexane volume ratio are 1.2 ~ 2:0.7 ~ 1.2:2.1 ~ 2.8；
3) microemulsion is prepared
The oily phase that step 2 obtains is measured, is added in beaker, and place the beaker in ultrasonic field, ultrasonic power is 100 ~ 300
W, ultrasonic time are 0.5 ~ 3h, then measure the water phase that step 1) obtains, water phase is added drop-wise to oil with the speed of 1 ~ 3 mL/min
Xiang Zhong after being added dropwise, stops after continuing 0.5 ~ 1h of ultrasonic disperse, obtains microemulsion, and the oil is mutually 15 with water phase volume ratio ~
2:1；
4) solvent-thermal process method prepares anatase titanium dioxide monocrystalline
The microemulsion that step 3) is obtained is transferred in hydrothermal reaction kettle, and reaction kettle is placed in 160 ~ 180 DEG C of drying box,
It after reacting 12 ~ 14 h, is cooled to room temperature, then filters, collect sediment；Sediment is successively used into dehydrated alcohol and deionized water
Washing is to neutrality, and in 60 DEG C of dry 12 h, grinding is finally placed in 450 ~ 550 DEG C of Muffle 1 ~ 3h of kiln roasting, obtains Detitanium-ore-type
Titanium dioxide single crystalline.
2. the preparation method of anatase titanium dioxide monocrystalline according to claim 1, which is characterized in that institute in step 1)
Triton x-100, n-hexyl alcohol and the cyclohexane volume ratio stated are 1.5:1:2.5.
3. the preparation method of anatase titanium dioxide monocrystalline according to claim 1, which is characterized in that institute in step 3)
Stating oily is mutually 13 ~ 5:1 with water phase volume ratio.
4. the preparation method of anatase titanium dioxide monocrystalline according to claim 1, which is characterized in that institute in step 3)
The ultrasonic power stated is 200 ~ 300 W, and ultrasonic time is 0.5 ~ 1 h.
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