CN106268733B - A kind of monodimension nano stick is self-assembly of the preparation method of the shelly-shaped three-dimensional titanic oxide hollow microballoon of the chestnut with hierarchical structure - Google Patents
A kind of monodimension nano stick is self-assembly of the preparation method of the shelly-shaped three-dimensional titanic oxide hollow microballoon of the chestnut with hierarchical structure Download PDFInfo
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- CN106268733B CN106268733B CN201610820566.8A CN201610820566A CN106268733B CN 106268733 B CN106268733 B CN 106268733B CN 201610820566 A CN201610820566 A CN 201610820566A CN 106268733 B CN106268733 B CN 106268733B
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- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title claims abstract description 113
- 238000002360 preparation method Methods 0.000 title claims abstract description 26
- 241001070941 Castanea Species 0.000 title abstract description 15
- 235000014036 Castanea Nutrition 0.000 title abstract description 15
- 238000001338 self-assembly Methods 0.000 title abstract description 15
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 56
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims abstract description 44
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 39
- 238000001035 drying Methods 0.000 claims abstract description 3
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 claims abstract 2
- 229910052719 titanium Inorganic materials 0.000 claims description 35
- 239000010936 titanium Substances 0.000 claims description 34
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 32
- 238000003756 stirring Methods 0.000 claims description 28
- 239000002243 precursor Substances 0.000 claims description 24
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 18
- 238000006243 chemical reaction Methods 0.000 claims description 14
- 239000007787 solid Substances 0.000 claims description 13
- 238000001354 calcination Methods 0.000 claims description 12
- 238000010438 heat treatment Methods 0.000 claims description 11
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 11
- 235000019441 ethanol Nutrition 0.000 claims description 9
- 238000011049 filling Methods 0.000 claims description 9
- 230000035484 reaction time Effects 0.000 claims description 4
- -1 Titanium alkoxides Chemical class 0.000 claims description 3
- HKJYVRJHDIPMQB-UHFFFAOYSA-N propan-1-olate;titanium(4+) Chemical compound CCCO[Ti](OCCC)(OCCC)OCCC HKJYVRJHDIPMQB-UHFFFAOYSA-N 0.000 claims description 2
- 230000001699 photocatalysis Effects 0.000 abstract description 21
- 230000015556 catabolic process Effects 0.000 abstract description 11
- 238000006731 degradation reaction Methods 0.000 abstract description 11
- 239000003344 environmental pollutant Substances 0.000 abstract description 5
- 231100000719 pollutant Toxicity 0.000 abstract description 5
- 230000007062 hydrolysis Effects 0.000 abstract description 4
- 238000006460 hydrolysis reaction Methods 0.000 abstract description 4
- 238000004140 cleaning Methods 0.000 abstract 1
- 238000009833 condensation Methods 0.000 abstract 1
- 230000005494 condensation Effects 0.000 abstract 1
- 239000002904 solvent Substances 0.000 abstract 1
- 238000007146 photocatalysis Methods 0.000 description 17
- YYYARFHFWYKNLF-UHFFFAOYSA-N 4-[(2,4-dimethylphenyl)diazenyl]-3-hydroxynaphthalene-2,7-disulfonic acid Chemical compound CC1=CC(C)=CC=C1N=NC1=C(O)C(S(O)(=O)=O)=CC2=CC(S(O)(=O)=O)=CC=C12 YYYARFHFWYKNLF-UHFFFAOYSA-N 0.000 description 13
- 239000000463 material Substances 0.000 description 10
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 9
- 239000000047 product Substances 0.000 description 9
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 7
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 7
- 239000008367 deionised water Substances 0.000 description 7
- 229910021641 deionized water Inorganic materials 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- 239000004408 titanium dioxide Substances 0.000 description 7
- 239000002253 acid Substances 0.000 description 6
- 239000003054 catalyst Substances 0.000 description 6
- 239000013078 crystal Substances 0.000 description 6
- 230000002378 acidificating effect Effects 0.000 description 5
- 238000007654 immersion Methods 0.000 description 5
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 5
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 4
- 238000006555 catalytic reaction Methods 0.000 description 4
- 230000008859 change Effects 0.000 description 4
- 239000003973 paint Substances 0.000 description 4
- 238000004064 recycling Methods 0.000 description 4
- 238000000926 separation method Methods 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 230000007812 deficiency Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000012528 membrane Substances 0.000 description 3
- 239000003921 oil Substances 0.000 description 3
- 230000005855 radiation Effects 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 238000005215 recombination Methods 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 238000002835 absorbance Methods 0.000 description 2
- 238000013019 agitation Methods 0.000 description 2
- 230000004888 barrier function Effects 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 229910000019 calcium carbonate Inorganic materials 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 230000004087 circulation Effects 0.000 description 2
- 239000000356 contaminant Substances 0.000 description 2
- 235000013399 edible fruits Nutrition 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 230000004907 flux Effects 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 2
- 229910052753 mercury Inorganic materials 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 239000004005 microsphere Substances 0.000 description 2
- 239000002086 nanomaterial Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 230000006798 recombination Effects 0.000 description 2
- 238000005070 sampling Methods 0.000 description 2
- 239000011343 solid material Substances 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 206010016322 Feeling abnormal Diseases 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- HGWOWDFNMKCVLG-UHFFFAOYSA-N [O--].[O--].[Ti+4].[Ti+4] Chemical compound [O--].[O--].[Ti+4].[Ti+4] HGWOWDFNMKCVLG-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000010835 comparative analysis Methods 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 230000009647 facial growth Effects 0.000 description 1
- 238000005188 flotation Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 230000012010 growth Effects 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000012982 microporous membrane Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 238000003541 multi-stage reaction Methods 0.000 description 1
- 239000002073 nanorod Substances 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 239000003305 oil spill Substances 0.000 description 1
- 239000006250 one-dimensional material Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 230000000149 penetrating effect Effects 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000000985 reflectance spectrum Methods 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 238000009738 saturating Methods 0.000 description 1
- DCKVNWZUADLDEH-UHFFFAOYSA-N sec-butyl acetate Chemical compound CCC(C)OC(C)=O DCKVNWZUADLDEH-UHFFFAOYSA-N 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000012798 spherical particle Substances 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 229910021642 ultra pure water Inorganic materials 0.000 description 1
- 239000012498 ultrapure water Substances 0.000 description 1
- 238000000870 ultraviolet spectroscopy Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Classifications
-
- 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—
-
- B01J35/40—
-
- B01J35/51—
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/30—Particle morphology extending in three dimensions
- C01P2004/32—Spheres
- C01P2004/34—Spheres hollow
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/10—Photocatalysts
Abstract
The present invention relates to the preparation methods that a kind of monodimension nano stick is self-assembly of the shelly-shaped three-dimensional titanic oxide hollow microballoon of the chestnut with hierarchical structure, it is that water is generated by condensation of acetone, butyl titanate is promoted to hydrolyze, its hydrolysis rate and pattern are controlled by the way that hydrochloric acid is added, three-dimensional titanic oxide hollow microballoon is made through solvent heat again, by cleaning, be drying to obtain.In addition to efficient photocatalytic pollutant degradation ability, which also has good recyclability, and can be recycled for multiple times, and preparation process is simple, has broad application prospects in water treatment field.
Description
Technical field
The present invention relates to a kind of shelly-shaped three-dimensional dioxies of chestnut being self-assembly of by monodimension nano stick, with hierarchical structure
The preparation method for changing titanium tiny balloon, belongs to environment-friendly function field of nano material preparation.
Background technique
From 1792 by Japanese Scientists A.Fujishima and K.Honda in n-type semiconductor TiO2Water is had found on electrode
Photoelectrocatalysis decomposition after, TiO2Due to its preferable chemistry and physical stability, nontoxicity, low cost, environment friend
Good property, and widely applied to the fields such as photocatalysis, solar fuel cell, Photocatalyzed Hydrogen Production.
However, TiO2There is also many deficiencies, such as：TiO2Electron-hole recombination rate quickly, have report claim, electricity
For son-hole-recombination between p seconds several, the compound of carrier will be greatly reduced TiO2Photocatalytic Degradation Property.Meanwhile having
The TiO of excellent photocatalysis performance2Particle, diameter are mostly nanoscales, and recycling is difficult, and reuse ratio is low.It is living for photocatalysis
Property it is not high, recycle difficult deficiency, solution relatively good at present be prepare it is built-up by one-dimensional nano structure self assembly
Three-dimensional hierarchical structure TiO2.On the one hand, using its one-dimensional good carrier transmission performance of structures, electron-hole is reduced
Recombination rate improves photocatalytic activity；On the other hand, macroscopical micron order size, can by simple autoprecipitation or
Material is recycled in filtering, therefore can solve TiO2Photocatalytic activity is low and material recovery difficult problem.However, this
Class TiO2Material is mostly solid material, in water treatment applications, easily deposits to water bottom, and light wearing in polluted-water
Saturating power is very weak, so that TiO2It is low to the utilization rate of light, cause photocatalytic degradation capability low.This is easily precipitated not for solid material
Foot point has researcher by TiO2It is designed as hollow ball structure, polluted-water surface can be swum in, increase connects the sun
Touching, to improve photocatalysis performance.
Chinese patent document CN104671282A coats amorphous silica using calcium carbonate, then in silicon dioxide meter
Face deposition of titanium oxide is nanocrystalline, to get rutile titanium dioxide hollow sphere after removing calcium carbonate.However, suchlike
Hollow TiO2Preparation process is often more complicated, is related to multistep reaction, and operating condition is harsh, is not suitable for industrialized production,
And products therefrom is not formed by one-dimensional material self assembly, photocatalytic activity still has greatly improved space.
Summary of the invention
In view of the deficiencies of the prior art, the present invention provide it is a kind of it is being self-assembly of by monodimension nano stick, have classification knot
The preparation method of the shelly-shaped three-dimensional titanic oxide hollow microballoon of the chestnut of structure, the nanometer rods on the three-dimensional titanic oxide hollow microballoon surface
Structure is not only that carrier transfer provides path, accelerates the separation of electron-hole, and have good scattering and folding to incident light
The effect of penetrating, increases the utilization rate of light, to further increase photocatalysis efficiency.Meanwhile the hollow ball structure can float on dirt
Water surface is contaminated, preferably receives solar irradiation, and can be come into full contact with the pollutant that swims in water surface, such as oils,
Keep its degradation thorough.In addition, the three-dimensional titanic oxide hollow microballoon is micron order size, in conjunction with its flotation property, by simple
Ground barrier, that is, be able to achieve TiO2With the separation of water body, so that complicated separation and redisperse operation be omitted, processing water is directly arranged
When putting, TiO2Then retain and be reused in the reactor, and then extends TiO2Service life.
Technical scheme is as follows：
A kind of monodimension nano stick is self-assembled into the preparation method of the three-dimensional titanic oxide hollow microballoon with hierarchical structure, packet
Include that steps are as follows：
(1) under stirring condition, titanium precursors are added in acetone, obtain solution A；The molar ratio of titanium precursors and acetone is
1:10‐1:60；
(2) under stirring condition, hydrochloric acid is added in solution A, and continues to stir 10-30min, obtains solution B；Hydrochloric acid with it is molten
Titanium precursors molar ratio in liquid A is 4:1‐16:1；
(3) by solution B in 120-180 DEG C of hydro-thermal reaction 4-24h；
(4) after completion of the reaction, obtained solid is separated, cleans, then dries；
(5) sample after drying is self-assembled into get monodimension nano stick with hierarchical structure through 300-800 DEG C of calcining
Three-dimensional titanic oxide hollow microballoon.
, according to the invention it is preferred to, titanium precursors described in step (1) are Titanium alkoxides, more preferable titanium propanolate or titanium
Acid butyl ester.
, according to the invention it is preferred to, titanium precursors described in step (1) and acetone molar ratio are 1:20‐1:25.
, according to the invention it is preferred to, the molar ratio of hydrochloric acid and titanium precursors is 5 in step (2):1‐10:1；
Preferably, the concentration of hydrochloric acid is 25-37wt%.
, according to the invention it is preferred to, hydrothermal temperature described in step (3) is 150-180 DEG C, reaction time 4-
8h。
, according to the invention it is preferred to, hydro-thermal reaction described in step (3) carries out in water heating kettle, the filling of water heating kettle
Ratio is 50%-80%.
, according to the invention it is preferred to, obtained solid is cleaned using water and ethyl alcohol as medium in step (4).
, according to the invention it is preferred to, obtained solid is dried in step (4) at 50-105 DEG C.
, according to the invention it is preferred to, gained sample, calcination time 2-4h are calcined in step (5) at 400-700 DEG C.
, according to the invention it is preferred to, the rate of stirring described in step (1) and step (2) is 500-2000 revs/min.
The principle of the present invention：
During the reaction, condensation reaction occurs between acetone molecules and generates water, on the one hand water generated is titanium precursor
Body provides oxygen source, on the other hand titanium precursors is promoted to hydrolyze.The addition of hydrochloric acid can control titanium precursors hydrolysis rate with
And product morphology.Under strongly acidic conditions, the hydrolysis rate of titanium precursors reduces, and is conducive to TiO2Be self-assembly of pattern it is complicated but
Controllable rutile-type material.Meanwhile the chloride ion in hydrochloric acid can select to be adsorbed on rutile (110) crystal face, not only drop
The surface of low (110) crystal faces can, further suppress titanium atom in solution in the absorption of (110) crystal face, and then inhibit the crystal face
Growth promotes it along one-dimensional rod-like structure is formed in terms of [001], since three-dimensional globular structure has minimum free energy, and
Reaction rate is lower, and monodimension nano stick generated can be self-assembly of three-dimensional globular structure.Three-dimensional titanium dioxide generated
Titanium tiny balloon has good photocatalytic activity, and can float on the water surface, on the one hand can enhance the absorption of sunlight, another party
Face is convenient for recycling, in marine oil spill, oil leak, draining accident treatment, has great advantage.
Compared with prior art, the invention has the advantages that：
1, the three-dimensional titanium dioxide microballoon sphere in the present invention is hollow structure, and density is low, water surface can be floated on, in reality
During the water treatment applications of border, TiO can be greatly increased2Sun light utilization efficiency, and then improve photocatalysis efficiency.In addition, energy
Pollutant that is enough and floating on water surface, such as oils come into full contact with, and improve its degradation efficiency, while can also be by simple
Ground barrier, realizes TiO2With the separation of water, recycling for material is further realized.
2, in the present invention three-dimensional titanic oxide hollow microballoon surface monodimension nano stick structure, there is good carrier to pass
Defeated performance can effectively reduce the compound of electronics and hole, and then improve TiO2Photocatalysis performance.In addition, monodimension nano stick
Structure is well dispersed in the solution, is not susceptible to reunite, ensure that TiO2It is effectively contacted between pollutant and good
Illumination penetrance, thus can be further improved the photocatalysis performance of material.
3, the three-dimensional titanic oxide hollow microballoon in the present invention is rutile crystal type, and refractive index is high, and its surface is one-dimensional
Nanorod structure has good scattering and refraction action to incident light, and then can enhance the TiO2Material to the utilization rate of light,
And then improve TiO2Photocatalysis performance.
4, the three-dimensional titanic oxide hollow microballoon size in the present invention is more uniform, and partial size is micron order, convenient for recycling.
5, the hierarchical structure titanic oxide hollow microballoon preparation process route in the present invention is simple, and raw material are easy to get, and are easy to
It realizes large-scale production, has broad application prospects.
Detailed description of the invention
Fig. 1 is the scanning electron microscope (SEM) photograph of three-dimensional titanic oxide hollow microballoon made from the embodiment of the present invention 1.
Fig. 2 is the X-ray diffraction spectrogram of three-dimensional titanic oxide hollow microballoon made from the embodiment of the present invention 1.
Fig. 3 is the ultraviolet-visible of three-dimensional titanic oxide hollow microballoon and Degussa P25 made from the embodiment of the present invention 1
Diffusing reflection spectrum.
Fig. 4 is immersion and the lower three-dimensional titanic oxide hollow microballoon photocatalytic degradation acid scarlet light of external lighting type light source irradiation
Catalytic unit schematic diagram, wherein：A is immersion, and B is external lighting type.
Fig. 5 is that three-dimensional titanic oxide hollow microballoon made from the embodiment of the present invention 1 and Degussa P25 are ultraviolet in immersion
To acid scarlet Photocatalytic Degradation Property correlation curve under radiant irradiation.
Fig. 6 is that three-dimensional titanic oxide hollow microballoon made from the embodiment of the present invention 1 and Degussa P25 are ultraviolet in external lighting type
To acid scarlet photocatalytic degradation correlation curve under radiant irradiation.
Fig. 7 is that three-dimensional titanic oxide hollow microballoon made from the embodiment of the present invention 1 and Degussa P25 are molten in acid scarlet
Dispersion in liquid.
Fig. 8 is the strainability pair of three-dimensional titanic oxide hollow microballoon and Degussa P25 made from the embodiment of the present invention 1
Than.
Fig. 9 is that the light during three-dimensional titanic oxide hollow microballoon made from the embodiment of the present invention 1 is recycled for multiple times is urged
Change activity change situation.
Figure 10 is the scanning electron microscopic picture of microballoon made from comparative example 1 of the present invention.
Figure 11 is the scanning electron microscopic picture of sample made from comparative example 2 of the present invention.
Figure 12 is the scanning electron microscopic picture of three-dimensional titanic oxide hollow microballoon made from the embodiment of the present invention 2.
Specific embodiment
The present invention is explained further below by way of specific embodiment and in conjunction with attached drawing.It should be understood that these embodiments are only used
In illustrating the present invention rather than limit the scope of the invention.In addition, it should also be understood that, after reading the content taught by the present invention,
Those skilled in the art can make various changes or modification to the present invention, and such equivalent forms equally fall within right appended by the application
Claim limited range.
Raw materials used in embodiment is conventional raw material, and commercial products, device therefor is conventional equipment.
Water used in embodiment is the ultrapure water that conductivity is 18.2M Ω.
Embodiment 1
It is a kind of that by monodimension nano stick independently to fill the shelly-shaped three-dimensional titanium dioxide of chestnut being formed, with hierarchical structure hollow micro-
The preparation method of ball, including steps are as follows：
(1) under the conditions of stirring rate is 500 revs/min, tetrabutyl titanate is added in acetone, solution A, metatitanic acid are obtained
N-butyl and the molar ratio of acetone are 1:20；
(2) under the conditions of stirring rate is 500 revs/min, the concentrated hydrochloric acid of 37wt% is added in above-mentioned solution A, and is held
Continuous stirring 10min, obtains solution B, and hydrochloric acid and titanium precursors molar ratio are 5:1；
(3) solution B is transferred in hydrothermal reaction kettle, 8h is reacted at 150 DEG C, water heating kettle filling proportion is 60%；
(4) after completion of the reaction, obtained solid is separated, is respectively washed three times with deionized water and ethyl alcohol, done at 80 DEG C
Dry 12h；
(5) will dry gained sample after 500 DEG C of calcining 2h to get it is being self-assembly of by monodimension nano stick, have and divide
The shelly-shaped three-dimensional titanic oxide hollow microballoon of the chestnut of level structure.
Electronic Speculum observation is scanned to product made from the present embodiment, as shown in Figure 1, it can be seen that resulting materials are micro-
Meter level titanic oxide hollow microballoon, microsphere surface are made of the monodimension nano stick self assembly grown along the outside homogeneous radiation of core.
Microsphere diameter is 3.0-3.5 μm.
Fig. 2 is three-dimensional titanic oxide hollow microballoon X-ray diffraction spectrogram obtained by embodiment 1, it can be seen that embodiment
Three-dimensional titanic oxide hollow microballoon obtained by 1 is rutile TiO2(JCPDS NO.21-1276), and 27.5,36.1,
39.2,41.3,44.1,54.3,56.6,62.9,69.1 respectively correspond rutile TiO2(110), (101), (200),
(111), (210), (211), (220), (002), (301) and (112) crystal face.
Fig. 3 is three-dimensional titanic oxide hollow microballoon obtained by embodiment 1 and Degussa P25 (hereinafter referred to as P25)
Ultraviolet-visible diffuse reflectance spectrum figure, it can be seen that apparent Red Shift Phenomena has occurred compared with P25 in three-dimensional titanic oxide hollow microballoon,
Being primarily due to three-dimensional titanic oxide hollow microballoon obtained by embodiment 1 is Rutile Type, and P25 is anatase and rutile
Mixed phase, Rutile Type TiO2With Anatase TiO2Forbidden bandwidth be respectively (3.0eV) and (3.2eV), the change of forbidden bandwidth
It is narrow to bring bigger absorbing wavelength.
Test example 1：
It is tested by using photocatalytic degradation of the immersion ultraviolet source to acidic bright red paint, catalytic unit such as Fig. 4 A
It is shown.The contaminant degradation performance of the three-dimensional titanic oxide hollow microballoon of the classification obtained of comparative example 1 and P25 compare,
Photocatalysis experimental method is as follows：
Light-catalyzed reaction is in cylindrical glass container (cross section 80cm2, high 30cm) and it carries out under interior normal temperature and pressure, using light
Source immersion is reacted, and light source is the low pressure mercury lamp (14W) of dominant wavelength 254nm, using acidic bright red paint as simulating pollution
Object evaluates the contaminant-removal properties of catalyst.In experimentation, it is acid big that 100mg catalyst is put into 500ml first
In red solution (30mg/L), magnetic agitation 60 minutes under the conditions of being protected from light make acid scarlet reach absorption in catalyst surface and put down
Weighing apparatus；Later, light source is opened, after ultraviolet light, every 5 minutes sampling 5ml, after syringe filters filter, utilization was ultraviolet
Visible spectrophotometer measures the absorbance of filtrate, calculates the bright red concentration of remaining acid with this, and finds out photocatalytic degradation removal
Rate.
Three-dimensional titanic oxide hollow microballoon prepared by embodiment 1 all uses same experimental conditions to measure with P25.Test knot
Fruit is as shown in figure 5, as shown in Figure 5, in light-catalyzed reaction, the more three-dimensional titanic oxide hollow microballoon of Preliminary degradation efficiency of P25
Slightly higher, but with the propulsion in reaction time, the two reaches unanimity substantially to the degradation efficiency of dyestuff, and when 60min, degradation efficiency is all
Close to 100%.It is generally believed that the Photocatalytic activity of rutile TiO_2 is weak compared with anatase, but obtained three in embodiment 1
Dimension titanic oxide hollow microballoon but possesses good contaminant-removal properties, and two can be effectively prevented by being mostly derived from its hierarchical structure
Titan oxide particles are reunited, so that the contact area with pollutant is increased, in addition, monodimension nano stick structure provides for light induced electron
Good access, promotes the quick transmission of carrier, reduces the compound of photo-generate electron-hole, urge to improve light
Change performance.Meanwhile the structure of monodimension nano stick makes incident light be reflected and be scattered, and increases the utilization rate of light, thus into
One step improves photocatalysis performance.
Test example 2：
It is tested by using photocatalytic degradation of the external lighting type ultraviolet source vertical irradiation to acidic bright red paint, catalysis dress
It sets as shown in Figure 4 B.To the contaminant degradation performance of three-dimensional titanic oxide hollow microballoon made from embodiment 1 and Degussa P25
It compares, photocatalysis experimental method is as follows：
Light-catalyzed reaction is in cylindrical glass container (cross section 50cm2, high 5cm) and it carries out under interior normal temperature and pressure, using outer
Illuminated light source vertical irradiation, light source is the low pressure mercury lamp (14W) of dominant wavelength 254nm, using acidic bright red paint as simulating pollution
Object evaluates the contaminant-removal properties of catalyst.In experimentation, 20mg catalyst is put into 100ml acid scarlet first
In solution (30mg/L), magnetic agitation 60 minutes, make acid scarlet reach adsorption equilibrium in catalyst surface under the conditions of being protected from light；
Later, light source is opened, every 5 minutes sampling 5ml, after syringe filters filter, utilizes ultraviolet-uisible spectrophotometer, measurement
The absorbance of filtrate calculates the bright red concentration of remaining acid with this, and finds out light degradation removal rate.
Three-dimensional titanic oxide hollow microballoon prepared by embodiment 1 all uses same experimental conditions to measure with P25.Test knot
Fruit is as shown in fig. 6, it will be appreciated from fig. 6 that the photocatalysis of acid scarlet drops in three-dimensional titanic oxide hollow microballoon prepared by embodiment 1
It solves performance and is better than P25.
Fig. 7 is that three-dimensional titanic oxide hollow microballoon made from embodiment 1 and P25 are floating feelings in acid scarlet solution surface
Condition photo, it can be seen that three-dimensional titanic oxide hollow microballoon can float on liquid surface well, under same reaction conditions,
It is higher to the utilization rate of external lighting type light source, therefore show the contaminant-removal properties more more excellent than P25.
It is tested by filtering with microporous membrane, to the filterability of three-dimensional titanic oxide hollow microballoon and P25 made from embodiment 1
It can be carried out comparative analysis.Fig. 8 is the strainability comparison of the two.As can be seen that under identical transmembrane pressure, prepared three-dimensional two
The membrane flux of titanium oxide tiny balloon is much larger than P25, and with the continuous increase of TMP, membrane flux linearly constantly increases, explanation
The material has good recyclability.
It disperses the three-dimensional titanic oxide hollow microballoon that filter membrane is retained in after filtration experiment in acid scarlet solution again,
It repeats photocatalysis described in test example 2 to test, after photocatalysis 1h, is filtered test again, so recycle, observation circulation
In the process when photocatalysis 1h acid scarlet degradation efficiency variation, investigate the photocatalytic activity stability of material prepared.Such as Fig. 9
It is shown, it can be seen that by 6 circulations, in ultraviolet source under external vertical radiation situation, prepared three-dimensional titanium dioxide
Titanium tiny balloon is still up to 50% to the photocatalytic degradation efficiency of acid scarlet, and P25 to the degradation efficiency of acid scarlet according to
Secondary reduction, it is seen then that three-dimensional titanic oxide hollow microballoon has good photocatalysis stability.
Comparative example 1
The preparation method of sample, including steps are as follows：
(1) under the conditions of stirring rate is 1000 revs/min, tetrabutyl titanate is added in acetone, solution A, titanium are obtained
Sour N-butyl and the molar ratio of acetone are 1:20；
(2) under the conditions of stirring rate is 500 revs/min, the concentrated hydrochloric acid of 37wt% is added in above-mentioned solution A, and is held
Continuous stirring 10min, obtains solution B；Hydrochloric acid and titanium precursors molar ratio are 20:1；
(3) solution B is transferred in hydrothermal reaction kettle, 8h is reacted at 150 DEG C, water heating kettle filling proportion is 60%；
(4) after completion of the reaction, obtained solid is separated, is respectively washed three times with deionized water and ethyl alcohol, done at 80 DEG C
Dry 12h；
(5) sample obtained by will be dry is after 500 DEG C of calcining 2h to get sample.
Electronic Speculum observation is scanned to product made from this comparative example, as shown in Figure 10, it can be seen that concentrated hydrochloric acid molar ratio
When excessively high, hollow shell structure disappears, and stick is from the uniform outside radiation growth of core, between stick and stick when lower concentrated hydrochloric acid molar ratio more
Crypto set, it is seen that concentrated hydrochloric acid dosage is of great significance to control product morphology.
Comparative example 2
The preparation method of sample, including steps are as follows：
(1) under the conditions of stirring rate is 1000 revs/min, tetrabutyl titanate is added in acetone, solution A, titanium are obtained
Sour N-butyl and the molar ratio of acetone are 1:20；
(2) under the conditions of stirring rate is 500 revs/min, the concentrated hydrochloric acid of 37wt% is added in above-mentioned solution A, and is held
Continuous stirring 10min, obtains solution B；Hydrochloric acid and titanium precursors molar ratio are 2.5:1；
(3) solution B is transferred in hydrothermal reaction kettle, 8h is reacted at 150 DEG C, water heating kettle filling proportion is 60%；
(4) after completion of the reaction, obtained solid is separated, is respectively washed three times with deionized water and ethyl alcohol, done at 80 DEG C
Dry 12h；
(5) sample obtained by will be dry is after 500 DEG C of calcining 2h to get sample.
Electronic Speculum observation is scanned to product made from this comparative example, as shown in figure 11, it can be seen that concentrated hydrochloric acid molar ratio
When too low, the hydrolysis rate of TiO 2 precursor is unable to get effective control, and obtained sample is for no hollow shell and without rodlike
The irregular pattern of structure.
Embodiment 2
It is a kind of that by monodimension nano stick independently to fill the shelly-shaped three-dimensional titanium dioxide of chestnut being formed, with hierarchical structure hollow micro-
The preparation method of ball, including steps are as follows：
(1) under the conditions of stirring rate is 1000 revs/min, tetrabutyl titanate is added in acetone, solution A, titanium are obtained
Sour N-butyl and the molar ratio of acetone are 1:20.
(2) under the conditions of stirring rate is 500 revs/min, the concentrated hydrochloric acid of 37wt% is added in above-mentioned solution A, and is held
Continuous stirring 10min, obtains solution B；Hydrochloric acid and titanium precursors molar ratio are 5:1
(3) solution B is transferred in hydrothermal reaction kettle, 8h is reacted at 180 DEG C, water heating kettle filling proportion is 70%.
(4) after completion of the reaction, obtained solid is separated, is respectively washed three times with deionized water and ethyl alcohol, done at 105 DEG C
Dry 8h.
(5) will dry gained sample after 400 DEG C of calcining 3h to get it is being self-assembly of by monodimension nano stick, have and divide
The shelly-shaped three-dimensional titanic oxide hollow microballoon of the chestnut of level structure.
Electronic Speculum observation is scanned to product made from the present embodiment, as shown in figure 12, it can be seen that in higher reaction temperature
Under the conditions of degree and longer reaction time, hollow shell structure is still remained, however the club shaped structure on hollow shell surface changes,
There is spherical particle aggregation in end, therefore, during preparing three-dimensional titanic oxide hollow microballoon, reaction temperature and time pair
There is great influence in product morphology.
Embodiment 3
It is a kind of that by monodimension nano stick independently to fill the shelly-shaped three-dimensional titanium dioxide of chestnut being formed, with hierarchical structure hollow micro-
The preparation method of ball, including steps are as follows：
(1) under the conditions of stirring rate is 1000 revs/min, tetrabutyl titanate is added in acetone, solution A, titanium are obtained
Sour N-butyl and the molar ratio of acetone are 1:10；
(2) under the conditions of stirring rate is 1000 revs/min, the concentrated hydrochloric acid of 37wt% is added in above-mentioned solution A, and is held
Continuous stirring 10min, obtains solution B, and hydrochloric acid and titanium precursors molar ratio are 8:1；
(3) solution B is transferred in hydrothermal reaction kettle, is reacted at 120 DEG C for 24 hours, water heating kettle filling proportion is 60%；
(4) after completion of the reaction, obtained solid is separated, is respectively washed three times with deionized water and ethyl alcohol, done at 80 DEG C
Dry 12h；
(5) will dry gained sample after 400 DEG C of calcining 4h to get it is being self-assembly of by monodimension nano stick, have and divide
The shelly-shaped three-dimensional titanic oxide hollow microballoon of the chestnut of level structure.
Embodiment 4
It is a kind of that by monodimension nano stick independently to fill the shelly-shaped three-dimensional titanium dioxide of chestnut being formed, with hierarchical structure hollow micro-
The preparation method of ball, including steps are as follows：
(1) under the conditions of stirring rate is 1500 revs/min, tetrabutyl titanate is added in acetone, solution A, titanium are obtained
Sour N-butyl and the molar ratio of acetone are 1:60；
(2) under the conditions of stirring rate is 1500 revs/min, the concentrated hydrochloric acid of 37wt% is added in above-mentioned solution A, and is held
Continuous stirring 10min, obtains solution B, and hydrochloric acid and titanium precursors molar ratio are 15:1；
(3) solution B is transferred in hydrothermal reaction kettle, 10h is reacted at 150 DEG C, water heating kettle filling proportion is 60%；
(4) after completion of the reaction, obtained solid is separated, is respectively washed three times with deionized water and ethyl alcohol, done at 80 DEG C
Dry 12h；
(5) will dry gained sample after 700 DEG C of calcining 3h to get it is being self-assembly of by monodimension nano stick, have and divide
The shelly-shaped three-dimensional titanic oxide hollow microballoon of the chestnut of level structure.
Embodiment 5
It is a kind of that by monodimension nano stick independently to fill the shelly-shaped three-dimensional titanium dioxide of chestnut being formed, with hierarchical structure hollow micro-
The preparation method of ball, including steps are as follows：
(1) under the conditions of stirring rate is 800 revs/min, tetrabutyl titanate is added in acetone, solution A, metatitanic acid are obtained
N-butyl and the molar ratio of acetone are 1:40；
(2) under the conditions of stirring rate is 800 revs/min, the concentrated hydrochloric acid of 37wt% is added in above-mentioned solution A, and is held
Continuous stirring 10min, obtains solution B, and hydrochloric acid and titanium precursors molar ratio are 10:1；
(3) solution B is transferred in hydrothermal reaction kettle, 15h is reacted at 130 DEG C, water heating kettle filling proportion is 60%；
(4) after completion of the reaction, obtained solid is separated, is respectively washed three times with deionized water and ethyl alcohol, done at 80 DEG C
Dry 12h；
(5) will dry gained sample after 600 DEG C of calcining 3h to get it is being self-assembly of by monodimension nano stick, have and divide
The shelly-shaped three-dimensional titanic oxide hollow microballoon of the chestnut of level structure.
Claims (9)
1. a kind of monodimension nano stick is self-assembled into the preparation method of the three-dimensional titanic oxide hollow microballoon with hierarchical structure, including
Steps are as follows：
（1）Under stirring condition, titanium precursors are added in acetone, obtain solution A；The molar ratio of titanium precursors and acetone is 1:
10-1:60；
（2）Under stirring condition, it is that 37wt% hydrochloric acid is added in solution A, and continues to stir 10-30min by concentration, obtains solution B；
Titanium precursors molar ratio in hydrochloric acid and solution A is 4:1-16:1；
（3）By solution B in 120-180 DEG C of hydro-thermal reaction 4-24h；
（4）After completion of the reaction, obtained solid is separated, cleans, then dries；
（5）Sample after drying is self-assembled into the three-dimensional with hierarchical structure through 300-800 DEG C of calcining to get monodimension nano stick
Titanic oxide hollow microballoon.
2. monodimension nano stick according to claim 1 is self-assembled into the three-dimensional titanic oxide hollow microballoon with hierarchical structure
Preparation method, which is characterized in that step（1）Described in titanium precursors be Titanium alkoxides.
3. monodimension nano stick according to claim 2 is self-assembled into the three-dimensional titanic oxide hollow microballoon with hierarchical structure
Preparation method, which is characterized in that step（1）Described in Titanium alkoxides be titanium propanolate or butyl titanate.
4. monodimension nano stick according to claim 1 is self-assembled into the three-dimensional titanic oxide hollow microballoon with hierarchical structure
Preparation method, which is characterized in that step（1）Described in titanium precursors and acetone molar ratio be 1:20-1:25.
5. monodimension nano stick according to claim 1 is self-assembled into the three-dimensional titanic oxide hollow microballoon with hierarchical structure
Preparation method, which is characterized in that step（2）The molar ratio of middle hydrochloric acid and titanium precursors is 5:1-10:1.
6. monodimension nano stick according to claim 1 is self-assembled into the three-dimensional titanic oxide hollow microballoon with hierarchical structure
Preparation method, which is characterized in that step（3）Described in hydrothermal temperature be 150-180 DEG C, reaction time 4-8h.
7. monodimension nano stick according to claim 1 is self-assembled into the three-dimensional titanic oxide hollow microballoon with hierarchical structure
Preparation method, which is characterized in that step（3）Described in hydro-thermal reaction carried out in water heating kettle, the filling proportion of water heating kettle
For 50%-80%.
8. monodimension nano stick according to claim 1 is self-assembled into the three-dimensional titanic oxide hollow microballoon with hierarchical structure
Preparation method, which is characterized in that step（4）In by medium of water and ethyl alcohol clean obtained solid；
Step（4）In at 50-105 DEG C dry obtained solid.
9. monodimension nano stick according to claim 1 is self-assembled into the three-dimensional titanic oxide hollow microballoon with hierarchical structure
Preparation method, which is characterized in that step（5）In at 400-700 DEG C calcining gained sample, calcination time 2-4h.
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| EP0687199B1 (en) * | 1993-03-05 | 1997-06-04 | Solvay Deutschland GmbH | Method of producing spherical particles |
| CN103151176A (en) * | 2013-03-08 | 2013-06-12 | 厦门大学 | Method for preparing three-dimensional spherical anatase type TiO2 photo-anode |
| CN103523827A (en) * | 2013-09-29 | 2014-01-22 | 中国科学院苏州纳米技术与纳米仿生研究所 | Preparation method of three-dimensional dendritic TiO2 (titanium dioxide) array with rapid electronic transmission performance |
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| EP0687199B1 (en) * | 1993-03-05 | 1997-06-04 | Solvay Deutschland GmbH | Method of producing spherical particles |
| CN103151176A (en) * | 2013-03-08 | 2013-06-12 | 厦门大学 | Method for preparing three-dimensional spherical anatase type TiO2 photo-anode |
| CN103523827A (en) * | 2013-09-29 | 2014-01-22 | 中国科学院苏州纳米技术与纳米仿生研究所 | Preparation method of three-dimensional dendritic TiO2 (titanium dioxide) array with rapid electronic transmission performance |
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