CN107253736A - 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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- CN107253736A CN107253736A CN201710702635.XA CN201710702635A CN107253736A CN 107253736 A CN107253736 A CN 107253736A CN 201710702635 A CN201710702635 A CN 201710702635A CN 107253736 A CN107253736 A CN 107253736A
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- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title claims abstract description 98
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 239000012071 phase Substances 0.000 claims abstract description 36
- 239000008346 aqueous phase Substances 0.000 claims abstract description 27
- 239000004408 titanium dioxide Substances 0.000 claims abstract description 26
- 239000004530 micro-emulsion Substances 0.000 claims abstract description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 14
- 238000000034 method Methods 0.000 claims abstract description 13
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 12
- 239000010936 titanium Substances 0.000 claims abstract description 12
- 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 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
- 239000003153 chemical reaction reagent Substances 0.000 claims abstract description 8
- 230000001376 precipitating effect Effects 0.000 claims abstract description 8
- 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 6
- 230000008569 process Effects 0.000 claims abstract description 5
- 239000013049 sediment Substances 0.000 claims description 13
- ZSIAUFGUXNUGDI-UHFFFAOYSA-N hexan-1-ol Chemical compound CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 claims description 12
- 238000003756 stirring Methods 0.000 claims description 10
- GPRLSGONYQIRFK-MNYXATJNSA-N triton Chemical compound [3H+] GPRLSGONYQIRFK-MNYXATJNSA-N 0.000 claims description 10
- 238000006243 chemical reaction Methods 0.000 claims description 9
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- 230000035484 reaction time Effects 0.000 claims description 6
- 238000000227 grinding Methods 0.000 claims description 5
- 238000000967 suction filtration Methods 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- 239000007864 aqueous solution Substances 0.000 claims description 4
- 239000008367 deionised water Substances 0.000 claims description 4
- 229910021641 deionized water Inorganic materials 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 claims description 2
- 239000002245 particle Substances 0.000 abstract description 14
- 230000001699 photocatalysis Effects 0.000 abstract description 12
- 238000009826 distribution Methods 0.000 abstract description 7
- 239000000203 mixture Substances 0.000 abstract description 6
- 230000000694 effects Effects 0.000 abstract description 5
- -1 n-hexyl alcohols Chemical class 0.000 abstract description 4
- 239000006185 dispersion Substances 0.000 abstract description 2
- 239000003054 catalyst Substances 0.000 description 11
- 238000013019 agitation Methods 0.000 description 8
- 239000007788 liquid Substances 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- 235000019441 ethanol Nutrition 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 238000007146 photocatalysis Methods 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- OXAUNDBQHKIUSD-UHFFFAOYSA-N azanium;titanium;fluoride Chemical class [NH4+].[F-].[Ti] OXAUNDBQHKIUSD-UHFFFAOYSA-N 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
- 239000003643 water by type Substances 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
- 230000015556 catabolic process Effects 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 230000001276 controlling effect Effects 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 231100001261 hazardous Toxicity 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
- 239000004094 surface-active agent Substances 0.000 description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 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
- 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
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 239000004064 cosurfactant Substances 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
- 238000001514 detection method 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
- 238000005530 etching 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
- 230000006872 improvement Effects 0.000 description 1
- 238000003760 magnetic stirring Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000005259 measurement 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
- 238000006552 photochemical reaction Methods 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 239000013641 positive control Substances 0.000 description 1
- 230000001105 regulatory effect Effects 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
- 239000000126 substance Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000009885 systemic effect Effects 0.000 description 1
- 238000000870 ultraviolet spectroscopy Methods 0.000 description 1
Classifications
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- 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
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a kind of preparation method of anatase titanium dioxide monocrystalline.This method is using ammonium titanium fluoride as titanium source, using urea as precipitating reagent, and in the Reverse Microemulsion System that Qula leads to 100/ n-hexyl alcohols of X/hexamethylene/water composition, anatase titanium dioxide monocrystalline is prepared using solvent-thermal process method.The microjet that the present invention is produced by using the cavitation effect of ultrasonic wave, make oil phase be mixed with water and uniformly, so as to control particle diameter and distribution of the aqueous phase in oil phase, it is to avoid 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, and purity is high, free from admixture, with preferable photocatalytic activity.
Description
Technical field
The present invention relates to photochemical catalyst field, more particularly to a kind of preparation method of anatase titanium dioxide monocrystalline.
Background technology
TiO2Due to high photocatalytic activity, strong, environment-friendly fast light corrosive power, relative low price and to people
A kind of the advantages of body is non-toxic, it has also become semi-conducting material that people are most interested in photocatalytic pollutant degradation field.TiO2
There are three kinds of crystalline structures：Detitanium-ore-type, rutile-type and brookite type.Brookite type belongs to rhombic system, and photocatalytic activity is low, is
A kind of metastable state, research is seldom at present.Around Detitanium-ore-type and rutile TiO2Substantial amounts of research is done.Rutile TiO2
Heat resistance, heat endurance, chemical stability are superior to Detitanium-ore-type TiO2, can be widely applied to coating, paint, cosmetics, modeling
The fields such as material；And during 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, Yang etc. was in nature, 2008,453 (29):Reported in 638 with the relatively low TiF of hydrolysis rate4For
Titanium source, using HF as pattern controlling agent, using hydro-thermal method, has synthesized micron order Detitanium-ore-type TiO2Monocrystalline.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 employ HF (hydrofluoric acid) to obtain TiO2Monocrystalline.And HF is a kind of liquid with aggressive, directly
It is relatively hazardous using HF, the problems such as having etching apparatus and pollution environment.
The content of the invention
For deficiencies of the prior art, it is an object of the invention to provide a kind of anatase titanium dioxide list
Brilliant preparation method, it is to avoid using the liquid HF of aggressive, solve the problems such as equipment corrosion and environmental pollution.
To achieve the above object, the present invention is adopted the following technical scheme that：A kind of preparation of anatase titanium dioxide monocrystalline
Method, it is characterised in that comprise the following steps：
1) aqueous phase is prepared
Compound concentration is the aqueous solution of 300g/L titanium source, and precipitating reagent is then weighed in proportion and is added to the titanium source aqueous solution
In, magnetic stirrer stirs 1~3h, obtains aqueous phase, and the mol ratio of the titanium source and precipitating reagent is 1：3~10；
2) oil 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 oil phase, and the triton x-100, n-hexyl alcohol and hexamethylene volume ratio are 1.2~2：0.7~1.2：2.1~2.8；
3) microemulsion is prepared
Measure step 2) obtained oil phase, it is added in beaker, and beaker is placed in ultrasonic field, ultrasonic power is 100
~300W, ultrasonic time is 0.5~3h, then measures step 1) obtained aqueous phase, aqueous phase is dripped with 1~3mL/min speed
It is added in oil phase, after completion of dropping, continues to stop after 0.5~1h of ultrasonic disperse, obtain microemulsion, the oil phase and aqueous phase volume
Than for 15~2：1；
4) solvent-thermal process method prepares anatase titanium dioxide monocrystalline
By step 3) obtained microemulsion is transferred in hydrothermal reaction kettle, and reactor is placed in 120~200 DEG C of drying
In case, after 8~16h of reaction, room temperature is cooled to, then suction filtration, collects sediment；By sediment successively with absolute ethyl 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
Ore deposit type titanium dioxide single crystalline.
Further, step 1) described in titanium source be ammonium titanium fluoride, the precipitating reagent is urea, and ammonium titanium fluoride rubs with urea
You are than being 1：4~8.
Further, step 1) described in triton x-100, n-hexyl alcohol and hexamethylene volume ratio be 1.5：1：2.5.
Further, step 3) described in oil phase and aqueous phase volume ratio be 13~5：1.
Further, step 3) described in ultrasonic power be 200~300W, ultrasonic time be 0.5~1h.
Further, step 4) described in drying box reaction temperature be 150~180 DEG C, 12~14h of reaction time.
Compared with prior art, the present invention has the advantages that：
1st, 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 the Reverse Microemulsion System of alcohol/hexamethylene/water composition, anatase titanium dioxide monocrystalline is prepared using solvent-thermal process method,
Avoid using HF, safety and environmental protection, to human body and environment non-hazardous.With simple to operate.
2nd, the present invention prepares titanium dioxide single crystalline using ultrasound-microemulsion-solvent-thermal process method.Microemulsion be by oil phase and
The thermodynamically stable system of aqueous phase stirring.Wherein, oil phase is by surfactant, cosurfactant and continuous phase group
Into aqueous 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 are combined, and lipophilic group and oil phase are combined, and such aqueous phase is formed " reaction in oil phase
Device ", by agitation, promotes to form and countless small has been even up to micron or nano level " microreactor ".By using
The microjet that the cavitation effect of ultrasonic wave is produced, big " microreactor " is smashed, and oil phase is mixed with water and uniformly, so as to control
" microreactor " particle diameter and distribution are made, and then makes obtained titanium dioxide single crystalline grain diameter uniform.
3rd, the present invention is further by regulating and controlling the volume ratio of oil phase and aqueous phase, the rate of addition of aqueous phase, ultrasonic power, reaction
Temperature and the optimization in reaction time, to control TiO2Single crystal grain size distribution situation and reunion degree.The present invention prepare two
Titanium oxide monocrystalline particle diameter is evenly distributed, good dispersion, almost the reunion without particle, with preferable photocatalytic activity.
Brief description of the drawings
Fig. 1 is the SEM phenograms of the titanium dioxide single crystalline prepared in embodiment 1；
Fig. 2 is the SEM phenograms of the titanium dioxide single crystalline prepared in embodiment 2；
Fig. 3 is the SEM phenograms of the titanium dioxide single crystalline prepared in embodiment 3；
Fig. 4 is the titanium dioxide single crystalline XRD detection figures that prepare 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).
Embodiment
The present invention is described in further detail with reference to specific embodiments and the drawings.
First, a kind of preparation method of anatase titanium dioxide monocrystalline
Embodiment 1：
1) 1.5g ammonium titanium fluorides are weighed to be added in the beaker for filling 5mL deionized waters, stirs to whole dissolvings, adds
1.8g urea, stirs to whole dissolvings, is used as microemulsion aqueous phase.
2) 12mL triton x-100s, 8mL n-hexyl alcohols and 20mL hexamethylenes are measured, is added sequentially in 250mL beaker,
1~3h of magnetic agitation, is presented transparent homogeneous to solution, is used as microemulsion oil phase.
3) by step 2) obtained oil phase, it is placed in ultrasonic field, ultrasonic power is 300W, then by aqueous phase with 1mL/min
Speed be evenly added drop-wise in the oil phase being stirred continuously, after completion of dropping, continue ultrasonic disperse 1h, formed it is translucent homogeneous
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 subsequently cooled to room temperature.
5) supernatant liquor in hydrothermal reaction kettle is removed, suction filtration is carried out to remaining solid-liquid mixture, collect sediment；
6) by step 5) obtained sediment washs several times with absolute ethyl alcohol and deionized water successively, until during filtrate is in
Property；
7) by step 6) washing after sediment at 60 DEG C dry 12h；
8) by step 7) after the grinding of obtained product, 500 DEG C of Muffle kiln roasting 2h is put into, 1# titanium dioxide lists are made
It is brilliant.
Embodiment 2
1) 1.5g ammonium titanium fluorides are weighed to be added in the beaker for filling 5mL deionized waters, stirs to whole dissolvings, adds
1.8g urea, stirs to whole dissolvings, is used as microemulsion aqueous phase.
2) 12mL triton x-100s, 8mL n-hexyl alcohols and 20mL hexamethylenes are measured, is added sequentially in 250mL beaker,
1~3h of magnetic agitation, is presented transparent homogeneous to solution, is used as microemulsion oil phase.
3) by step 2) obtained oil phase, it is placed in ultrasonic field, ultrasonic power is 300W, by aqueous phase with 3mL/min speed
Degree is evenly added drop-wise in the oil phase being stirred continuously, after completion of dropping, continues ultrasonic disperse 1h, forms translucent homogeneous micro-
Emulsion.
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 subsequently cooled to room temperature.
5) supernatant liquor in hydrothermal reaction kettle is removed, suction filtration is carried out to remaining solid-liquid mixture, collect sediment；
6) by step 5) obtained sediment washs several times with absolute ethyl alcohol and deionized water successively, until during filtrate is in
Property；
7) by step 6) washing after sediment at 60 DEG C dry 12h；
8) by step 7) after the grinding of obtained product, 500 DEG C of Muffle kiln roasting 2h is put into, 2# titanium dioxide lists are made
It is brilliant.
Embodiment 3
1) 1.5g ammonium titanium fluorides are weighed to be added in the beaker for filling 5mL deionized waters, stirs to whole dissolvings, adds
1.8g urea, stirs to whole dissolvings, is used as microemulsion aqueous phase.
2) 12mL triton x-100s, 8mL n-hexyl alcohols and 20mL hexamethylenes are measured, is added sequentially in 250mL beaker,
1~3h of magnetic agitation, is presented transparent homogeneous to solution, is used as microemulsion oil phase.
3) by step 2) obtained oil phase, it is placed on magnetic stirring apparatus, aqueous phase is evenly added dropwise with 1mL/min speed
Into the oil phase being stirred continuously, after being added dropwise to complete, continue magnetic agitation 1h, form translucent homogeneous 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 subsequently cooled to room temperature.
5) supernatant liquor in hydrothermal reaction kettle is removed, suction filtration is carried out to remaining solid-liquid mixture, collect sediment；
6) by step 5) obtained sediment washs several times with absolute ethyl alcohol and deionized water successively, until during filtrate is in
Property；
7) by step 6) washing after sediment at 60 DEG C dry 12h；
8) by step 7) after the grinding of obtained product, 500 DEG C of Muffle kiln roasting 2h is put into, 3# titanium dioxide lists are made
It is brilliant.
2nd, the sign of titanium dioxide single crystalline and test
1st, the titanium dioxide single crystalline prepared in embodiment 1~3 is subjected to SEM signs respectively, obtains Fig. 1~3.
It will be seen from figure 1 that 1# titanium dioxide single crystallines particle is substantially spherical in octahedron, particle size distribution is more uniform,
And degree of reuniting is small；Figure it is seen that 2# titanium dioxide single crystalline particle size distributions are uneven, reunion degree is small；From figure
3 can be seen that, although the reunion degree of 3# titanium dioxide single crystalline particles is more serious.
After being mixed due to aqueous phase with oil phase, aqueous phase is formed in oil phase after " reactor ", magnetic stirrer, and
It can not be mixed with water oil phase and uniformly, make the reunion degree of obtained titanium dioxide single crystalline particle more serious；But by using
The microjet that the cavitation effect of ultrasonic wave is produced, first by agitation, promotes to form and countless small has been even up to micron
Or nano level " microreactor ".And then microjet smashes big " microreactor ", it is mixed with water oil phase and uniformly, makes system
The titanium dioxide single crystalline particle agglomeration degree obtained is small, and needs to be controlled oil phase rate of addition, so as to control " micro- reaction
Device " particle diameter and distribution, make obtained titanium dioxide single crystalline grain diameter uniform.As can be seen that rate of addition is 1mL/min when systems
The titanium dioxide single crystalline grain diameter obtained is substantially better than 3mL/min.
2nd, the D2PHASER types X-ray diffractometer manufactured using German Brooker company determines prepared by embodiment 1~3
Titanium dioxide single crystalline carries out XRD tests respectively.
Test condition is：Cu targets radiographic source (λ=0.154056nm), power is 30kV × 10mA, and measurement temperature is 25 DEG C,
Stride is 0.02s, and the residence time is 0.2s, and 2 θ angular regions of scanning are 10 °~80 °, obtain 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 materials, illustrates titanium dioxide single crystalline made from this method
For Detitanium-ore-type, and purity is high, free from admixture.
3rd, the photocatalysis performance evaluation of the titanium dioxide single crystalline prepared with embodiment 1~3 is limited in Beijing NewBide science and technology
The Phchem type III photochemical reactions instrument of company's production is carried out.The photocatalysis performance of sample is commented by degrading methyl orange solution
Valency.As a comparison, Degussa P25 are positive control as catalyst, are not added with catalyst for negative control, control group light degradation
Methyl orange experiment is also carried out under the conditions of same light photograph.Light source is the visible ray of 350W xenon lamps.Obtained two in embodiment 1~3
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 in 0.05g 1# catalyst, 2# catalyst, 3# catalyst and Degussa P25, blank sample and be not added with catalyst.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 350W xenon lamps (XE-JY500) irradiation
Lower progress photocatalysis test.A sample (each 4mL) is taken every 10min, is stopped to reaction 120min.The sample solution warp of taking-up
Centrifuge is centrifuged after 15min in 4000rpm, then with ultraviolet-visible spectrophotometer in wavelength is that first is tested 462nm at
The change in concentration of base orange solution.
From fig. 5, it is seen that obtained 1# and 2# catalyst has highest photocatalytic activity, higher than Degussa
P25.When 3# catalyst by aqueous phase because being added dropwise to oil phase, use magnetic agitation, make oil phase be mixed with water with it is uneven, finally
The reunion degree of obtained titanium dioxide single crystalline particle is more serious, and photocatalytic activity is less than Degussa P25.
The above embodiment of the present invention is only example to illustrate the invention, and is not the implementation to the present invention
The restriction of mode.For those of ordinary skill in the field, other can also be made not on the basis of the above description
With the change and variation of form.Here all embodiments can not be exhaustive.It is every to belong to technical scheme
Row of the obvious changes or variations amplified out still in protection scope of the present invention.
Claims (6)
1. a kind of preparation method of anatase titanium dioxide monocrystalline, it is characterised in that comprise the following steps：
1）Prepare aqueous phase
Compound concentration is the aqueous solution of 300 g/L titanium source, and precipitating reagent is then weighed in proportion and is added in the titanium source aqueous solution, magnetic
Power agitator stirring 1 ~ 3 h of stirring, obtains aqueous phase, and the mol ratio of the titanium source and precipitating reagent is 1：3~10；
2）Prepare oil phase
Triton x-100, n-hexyl alcohol and hexamethylene are measured respectively, and are added sequentially in beaker, magnetic stirrer 1 ~ 3
H, obtains oil phase, and the triton x-100, n-hexyl alcohol and hexamethylene volume ratio are 1.2 ~ 2：0.7~1.2：2.1~2.8；
3）Prepare microemulsion
Measure step 2）Obtained oil phase, is added in beaker, and beaker is placed in ultrasonic field, and ultrasonic power is 100 ~ 300
W, ultrasonic time is 0.5 ~ 3h, then measures step 1）Obtained aqueous phase, oil is added drop-wise to by aqueous phase with 1 ~ 3 mL/min speed
After Xiang Zhong, completion of dropping, continuing to stop after ultrasonic disperse 0.5 ~ 1h, obtain microemulsion, the oil phase and aqueous phase volume ratio be 15 ~
2：1；
4）Solvent-thermal process method prepares anatase titanium dioxide monocrystalline
By step 3）Obtained microemulsion is transferred in hydrothermal reaction kettle, and reactor is placed in 120 ~ 200 DEG C of drying box,
React after 8 ~ 16 h, be cooled to room temperature, then suction filtration, collect sediment；Sediment is used into absolute ethyl alcohol and deionized water successively
Washing is to neutrality, and in 60 DEG C of dry 12 h, grinding is finally placed in 450 ~ 550 DEG C of h of Muffle kiln roasting 1 ~ 3, obtains anatase
Type titanium dioxide single crystalline.
2. the preparation method of anatase titanium dioxide monocrystalline according to claim 1, it is characterised in that step 1）Middle institute
The titanium source stated is ammonium titanium fluoride, and the precipitating reagent is urea, and ammonium titanium fluoride is 1 with urea mol ratio：4~8.
3. the preparation method of anatase titanium dioxide monocrystalline according to claim 1, it is characterised in that step 1）Middle institute
Triton x-100, n-hexyl alcohol and the hexamethylene volume ratio stated are 1.5：1：2.5.
4. the preparation method of anatase titanium dioxide monocrystalline according to claim 1, it is characterised in that step 3）Middle institute
It is 13 ~ 5 that oil phase, which is stated, with aqueous phase volume ratio：1.
5. the preparation method of anatase titanium dioxide monocrystalline according to claim 1, it is characterised in that step 3）Middle institute
The ultrasonic power stated is 200 ~ 300 W, and ultrasonic time is 0.5 ~ 1 h.
6. the preparation method of anatase titanium dioxide monocrystalline according to claim 1, it is characterised in that step 4）Middle institute
The reaction temperature for the drying box stated is 160 ~ 180 DEG C, the h of reaction time 12 ~ 14.
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| CN107803900A (en) * | 2017-10-23 | 2018-03-16 | 东北林业大学 | A kind of preparation method of the feature timber with photocatalytic activity |
| WO2020155212A1 (en) * | 2019-02-01 | 2020-08-06 | 中国科学院福建物质结构研究所 | Titanium dioxide single-crystal material and growing method therefor |
| CN111994950A (en) * | 2020-09-14 | 2020-11-27 | 四川轻化工大学 | Preparation method of anatase type nano titanium dioxide microspheres |
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