CN104368328B - A kind of bismuth titanates strontium titanates photocatalysis composite granule and preparation method thereof - Google Patents
A kind of bismuth titanates strontium titanates photocatalysis composite granule and preparation method thereof Download PDFInfo
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- CN104368328B CN104368328B CN201410020025.8A CN201410020025A CN104368328B CN 104368328 B CN104368328 B CN 104368328B CN 201410020025 A CN201410020025 A CN 201410020025A CN 104368328 B CN104368328 B CN 104368328B
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Abstract
The invention discloses a kind of photocatalysis composite granule and preparation method thereof, the composite granule is with disc-shaped micron order Bi4Ti3O12Crystalline material is matrix, SrTiO3Particles coat is in Bi4Ti3O12Matrix surface is distributed between matrix material, and grain thickness is 100 200nm.The preparation method of the photocatalysis composite powder material include first by mol ratio be 2: 3 Bi2O3And TiO2With etc. quality KCl NaAfter Cl fused salts mixing and ball milling and drying, insert after sintering furnace is warming up to 1050 DEG C and be incubated 1h, remove fused salt after being cleaned by ultrasonic repeatedly using hot deionized water, dry and obtain Bi4Ti3O12Crystal.Again by Bi4Ti3O12Mixed in NaOH alkaline environments with strontium nitrate and Butyl Phthalate magnetic agitation, hydro-thermal lh~8h under the conditions of 200 DEG C, Bi is obtained after cooling, filtering, dry, heat treatment4Ti3O12/SrTiO3Photocatalysis composite granule.The photocatalysis composite granule technique of the present invention is simple, morphology controllable, with good photocatalysis performance, can the dyestuff such as degradation of methylene blue and methyl orange in the short time, available for giving up, in terms of sewage disposal.
Description
Technical field
The invention belongs to composite semiconductor material preparing technical field, and in particular to a kind of Bi4Ti3O12/SrTiO3Composite wood
Material and preparation method thereof.
Background of invention
The greatest problem that the 21 century mankind are faced is to realize economic and society sustainable development.Since 70 years 20th century
TiO is found for first Japanese Scientists Fujishima and Honda2After photoelectrolysis aquatic products hydrogen phenomenon on electrode, light is urged over more than 30 years
Change technology receives the extensive attention of domestic and foreign scholars, and the photochemical catalyst of excellent properties is in clean energy resource production, air cleaning, people
The new forms of energy new material fields such as work photosynthesis, photic super hydrophilic or super-hydrophobic, solar cell have larger application prospect.
To obtain the catalysis material with wide range visible absorption, on the one hand researcher reduces semiconductor band by band engineering
Gap and then increase visible absorption；On the other hand unknown visible-light photocatalysis material is tried to explore.
Firstly, for high-performance environment-friendly material TiO2System, main research includes the methods such as liquid phase method and electrochemistry
Synthesize dendroid, cellular, nanosphere, nanometer rods, nanobelt, nanometer sheet, the different morphologies such as nano wire and different orientation
TiO2；Construct TiO2The built in field of hetero-junctions is combined to suppress quantity of photogenerated charge, mainly including TiO2Each alternate hetero-junctions, TiO2
The hetero-junctions constituted with noble metal or carbon material；Other materials are to TiO2Doping and compound, the band structure of controlled material.Together
When, the new system such as sulfide, perovskite structure compound with special appearance and structure is also reported in succession, such as MoS2/
CdS, NaTaO3, Ba2In2O5/In2O3, BiVO4, the Ag in high activity face3PO4Deng all with higher visible light photocatalysis decomposition amount
Sub- efficiency, it has huge application prospect as Photocatalyzed Hydrogen Production material.
The content of the invention
Present invention offer is a kind of to have rock-steady structure concurrently and the NEW TYPE OF COMPOSITE powder body material of excellent photocatalysis performance, also provides
A kind of preparation method of controllable, the with low cost composite photocatalyst material of technique.
In order to solve the above technical problems, the technical solution adopted by the present invention is a kind of photocatalysis composite granule, it is described compound
Powder is with disc-shaped Bi4Ti3O12Material is matrix, described matrix compound coating submicron order SrTiO3Particle.
Present invention also offers a kind of preparation method of photocatalysis composite granule, including by mol ratio be 2: 3 Bi2O3With
TiO2With etc. quality KCl-NaCl fused salts mixing and ball milling and dry after, insert after sintering furnace is warming up to 1050 DEG C and be incubated 1h, make
Fused salt is removed after being cleaned by ultrasonic repeatedly with hot deionized water, drying obtains Bi4Ti3O12Crystal.Again by Bi4Ti3O12In NaOH or
KOH alkaline environments are mixed with 1g strontium nitrates and 2mL Butyl Phthalate magnetic agitations, hydro-thermal lh~8h under the conditions of 200 DEG C, cooling, mistake
Bi is obtained after filter, dry, 600 DEG C of heat treatments4Ti3O12/SrTiO3Photocatalysis composite powder material；
The photocatalysis composite powder material is that chemical formula is Bi4Ti3O12Matrix and chemical formula be SrTiO3Photocatalysis
Composite powder material；
Bi4Ti3O12Matrix material is disc-shaped profile, 3-5 μm of diameter, 0.5 μm of thickness, SrTiO3Particle diameter is 100-
200nm, is wrapped in matrix surface and is distributed between matrix.
In above-mentioned preparation method, described fused salt is KCl-NaCl.
In above-mentioned preparation method, the alkaline environment is NaOH.
In above-mentioned preparation method, it is preferred that the furnace atmosphere of the resistance furnace is air atmosphere, inert gas shielding gas
Atmosphere or vacuum.
Compared with prior art, the advantage of the invention is that：
(1) present invention is with Bi4Ti3O12For matrix, the photocatalysis performance of flaky matrix in itself is taken full advantage of, be make use of micro-
The characteristic that meter level powder is easily reclaimed, expands its application；Compound SrTiO3Particle has stable perovskite structure
With good photocatalysis performance, the two good forbidden band matching can suppress the compound of light induced electron and hole, and add multiple
Close the visible absorption scope of powder.
(2) present invention is using molten-salt growth method synthesizing micron-grade disc-shaped Bi4Ti3O12, make SrTiO in combination with hydro-thermal method3In base
Composite granule is obtained after nucleation and crystallization on body, heat treatment.Technological operation is convenient, and with low cost, composite powder material pattern is easy to
Control.
Brief description of the drawings
Fig. 1 is the SEM photograph on composite powder material surface prepared by the embodiment of the present invention 1.
Fig. 2 is the XRD spectra of composite powder material prepared by the embodiment of the present invention 1.
Fig. 3 is the EDS spectrograms of composite powder material prepared by the embodiment of the present invention 1.
Embodiment
Below in conjunction with Figure of description and specific preferred embodiment, the invention will be further described, but not therefore and
Limit the scope of the invention.
Embodiment 1：
A kind of photocatalysis composite granule of the invention, the composite is with disc-shaped micron order Bi4Ti3O12Crystalline material is
Matrix, Composite Sub-micro SrTiO between matrix surface and matrix3Material.
A kind of preparation method of the optic catalytic composite material of above-mentioned the present embodiment, comprises the following steps：
(1) by mol ratio be 2: 3 Bi2O3And TiO2With etc. the KCl-NaCl fused salts of quality mix, using absolute ethyl alcohol to be situated between
Matter, in planetary ball mill ball milling mixing 10h, is put into after drying 1h in drying box after slurry is sieved and obtains powder, by powder pressure
It is placed in fact in alumina ceramic crucible, 1h is incubated after being heated to 1050 DEG C in chamber type electric resistance furnace with 5 DEG C/min speed,
Fused salt is removed after being cleaned by ultrasonic repeatedly using hot deionized water, drying obtains Bi4Ti3O12Crystal.
(2) by Bi4Ti3O12With 1g strontium nitrates and 2mL Butyl Phthalate magnetic agitations in lmol/L NaOH alkaline environments
Mix, hydro-thermal 2h under the conditions of 200 DEG C, centrifugal filtration obtains sediment, will obtained after 600 DEG C of heat treatments of sediment drying after cooling
Bi4Ti3O12/SrTiO3Photocatalysis composite granule.
The above method of the present embodiment is successfully prepared photocatalysis composite granule.Fig. 1 is above-mentioned light manufactured in the present embodiment
The electron scanning micrograph of catalytic composite materials, it can be seen that Bi4Ti3O12Matrix is disc-shaped, and diameter is in 3-5 μ ms
Interior, piece strengthens the attachment for having submicron order on plane of crystal, and partial particulate is distributed between matrix material.Fig. 2 is the photocatalysis
The EDS figures of composite, it can be seen that flat crystal surface has strontium element.Fig. 3 is matrix material and optic catalytic composite material
XRD spectra, it can be seen that the main peak and Bi of matrix material4Ti3O12Characteristic peak is corresponded to completely, and Bi is removed in composite4Ti3O12
Outside characteristic peak, also occur and standard SrTiO3The corresponding peak of characteristic peak (JCPDS NO.35-0734), show to generate
Bi4Ti3O12/SrTiO3Composite.After tested, the optic catalytic composite material effect of the present embodiment is preferable, 3h under the conditions of natural light
The methylene blue of interior energy degraded more than 90%.
Embodiment 2：
A kind of photocatalysis composite granule of the invention, the composite is with disc-shaped micron order Bi4Ti3O12Crystalline material is
Matrix, Composite Sub-micro SrTiO between matrix surface and matrix3Material.
A kind of preparation method of the optic catalytic composite material of above-mentioned the present embodiment, the step of with embodiment 1 essentially identical, area
It is not only that, 1h is incubated after being heated to 1000 DEG C in chamber type electric resistance furnace with 5 DEG C/min speed in step (1).Obtain
Composite be disc-shaped profile, long a width of 3-5 μm, 0.5-1 μm of thickness.
Embodiment 3：
A kind of photocatalysis composite granule of the invention, the composite is with disc-shaped micron order Bi4Ti3O12Crystalline material is
Matrix, Composite Sub-micro SrTiO between matrix surface and matrix3Material.
A kind of preparation method of the optic catalytic composite material of above-mentioned the present embodiment, the step of with embodiment 1 essentially identical, area
It is not only that, 1h is incubated after being heated to 900 DEG C in chamber type electric resistance furnace with 5 DEG C/min speed in step (1).Obtain
Composite is square flake-like shape, long a width of 3-5 μm, 0.5-1 μm of thickness.
Embodiment 4：
A kind of photocatalysis composite granule of the invention, the composite is with disc-shaped micron order Bi4Ti3O12Crystalline material is
Matrix, Composite Sub-micro SrTiO between matrix surface and matrix3Material.
A kind of preparation method of the optic catalytic composite material of above-mentioned the present embodiment, the step of with embodiment 1 essentially identical, area
It is not only that, hydro-thermal 4h under the conditions of 200 DEG C in step (2).
Embodiment 5：
A kind of photocatalysis composite granule of the invention, the composite is with disc-shaped micron order Bi4Ti3O12Crystalline material is
Matrix, Composite Sub-micro SrTiO between matrix surface and matrix3Material.
A kind of preparation method of the optic catalytic composite material of above-mentioned the present embodiment, the step of with embodiment 1 essentially identical, area
It is not only that, without 600 DEG C of heat treatments after sediment drying in step (2).
Described above is only the preferred embodiment of the present invention, and protection scope of the present invention is not limited merely to above-mentioned implementation
Example.All technical schemes belonged under thinking of the present invention belong to protection scope of the present invention.It is noted that for the art
Those of ordinary skill for, improvements and modifications these improvements and modifications under the premise without departing from the principles of the invention should also be regarded
For protection scope of the present invention.
Claims (4)
1. a kind of preparation method of photocatalysis composite granule, including by Bi2O3And TiO2With etc. the KCl-NaCl fused salts of quality mix
After ball milling and drying, insert after sintering furnace is warming up to 1050 DEG C and be incubated 1h, use hot deionized water to be removed after being cleaned by ultrasonic repeatedly
Fused salt, drying obtains Bi4Ti3O12Crystal；Again by Bi4Ti3O12In NaOH or KOH alkaline environments and strontium nitrate and butyl titanate magnetic
Power stirring is mixed, hydro-thermal 1h-8h under the conditions of 200 DEG C, and Bi is obtained after cooling, filtering, dry, 600 DEG C of heat treatments4Ti3O12/
SrTiO3Photocatalysis composite powder material；
The photocatalysis composite powder material is that chemical formula is Bi4Ti3O12Matrix and chemical formula be SrTiO3Photocatalysis be combined
Powder body material；
Bi4Ti3O12Matrix material is disc-shaped profile, 3-5 μm of diameter, 0.5 μm of thickness, SrTiO3Particle diameter is 100-
200nm, is wrapped in matrix surface and is distributed between matrix.
2. a kind of preparation method of photocatalysis composite granule according to claim 1, it is characterised in that the fused salt is
KCl-NaCl。
3. a kind of preparation method of photocatalysis composite granule according to claim 1, it is characterised in that the alkaline environment
For NaOH.
4. the preparation method of a kind of photocatalysis composite granule according to claim 1, it is characterised in that the sintering furnace
Furnace atmosphere is air atmosphere, inert gas shielding atmosphere or vacuum.
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| CN105618030B (en) * | 2015-12-23 | 2018-03-20 | 东南大学 | A kind of high efficiency photocatalyst SrTiO3/Bi2WO6Preparation method and applications |
| CN105536772B (en) * | 2015-12-23 | 2018-03-20 | 东南大学 | A kind of preparation method of hetero-junctions nano-photocatalyst material and the application of the material |
| CN105618090B (en) * | 2016-01-07 | 2018-03-30 | 中国林业科学研究院林产化学工业研究所 | A kind of efficiently heterojunction ultraviolet photochemical catalyst and its preparation method and application |
| CN107262121A (en) * | 2017-07-20 | 2017-10-20 | 西安科技大学 | A kind of magnetic coupling visible light catalyst and preparation method thereof |
| CN109928422A (en) * | 2018-08-14 | 2019-06-25 | 华北理工大学 | A kind of method that fused salt prepares potassium titanate crystal |
| CN109999785A (en) * | 2019-05-13 | 2019-07-12 | 兰州理工大学 | Bi4Ti3O12/Bi2Ti2O7The preparation method of composite photo-catalyst |
| CN114939423A (en) * | 2022-06-24 | 2022-08-26 | 武汉科技大学 | Bi 4 Ti 3 O 12 /Bi 2 S 3 Piezoelectric photocatalyst and preparation method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101147859A (en) * | 2007-11-08 | 2008-03-26 | 北京师范大学 | Method for preparing porous bismuth titanate photocatalyst |
| CN101311376A (en) * | 2008-02-26 | 2008-11-26 | 浙江大学 | Method for preparing strontium titanate nanometer powder of one-dimensional structure |
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| PT104692B (en) * | 2009-07-29 | 2013-06-18 | Univ Do Minho | PHOTOCATALITICAL COATING FOR CONTROLLED RELEASE OF VOLATILE AGENTS |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101147859A (en) * | 2007-11-08 | 2008-03-26 | 北京师范大学 | Method for preparing porous bismuth titanate photocatalyst |
| CN101311376A (en) * | 2008-02-26 | 2008-11-26 | 浙江大学 | Method for preparing strontium titanate nanometer powder of one-dimensional structure |
Non-Patent Citations (3)
| Title |
|---|
| A simple method for fabricating p–n junction photocatalyst CuFe2O4/ Bi4Ti3O12 and its photocatalytic activity;W.Zhao,et al;《Materials Chemistry and Physics》;20131116;第143卷(第3期);文章第953页左栏第1-2段 * |
| Photocatalytic degradation efficacy of Bi4Ti3O12 micro-scale platelets over methylene blue under visible light;Wei Zhao,et al;《Journal of Physics and Chemistry of Solids》;20130614;第74卷(第11期);文章摘要，第1604页第2节，第1605页Fig.2 * |
| 原位水热合成SrTiO3/TiO2复合纳米纤维及光催化性能;李跃军等;《高等学校化学学报》;20111130;第32卷(第11期);文章第2490页第2段，第2491页1.2节，第2492页2.2节 * |
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