CN115403068B - Barium titanate nano cube material and preparation method and application thereof - Google Patents
Barium titanate nano cube material and preparation method and application thereof Download PDFInfo
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- JRPBQTZRNDNNOP-UHFFFAOYSA-N barium titanate Chemical compound [Ba+2].[Ba+2].[O-][Ti]([O-])([O-])[O-] JRPBQTZRNDNNOP-UHFFFAOYSA-N 0.000 title claims abstract description 71
- 229910002113 barium titanate Inorganic materials 0.000 title claims abstract description 71
- 239000000463 material Substances 0.000 title claims abstract description 53
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 239000013078 crystal Substances 0.000 claims abstract description 14
- 238000000034 method Methods 0.000 claims abstract description 13
- 238000006243 chemical reaction Methods 0.000 claims abstract description 12
- 238000001354 calcination Methods 0.000 claims abstract description 8
- 230000001699 photocatalysis Effects 0.000 claims abstract description 5
- 238000007146 photocatalysis Methods 0.000 claims abstract description 5
- 230000007613 environmental effect Effects 0.000 claims abstract description 4
- 238000000746 purification Methods 0.000 claims abstract description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 20
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 16
- 229910052788 barium Inorganic materials 0.000 claims description 11
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 claims description 11
- 239000010936 titanium Substances 0.000 claims description 11
- 229960000583 acetic acid Drugs 0.000 claims description 10
- 150000001875 compounds Chemical class 0.000 claims description 10
- 239000012362 glacial acetic acid Substances 0.000 claims description 10
- 229910052719 titanium Inorganic materials 0.000 claims description 9
- -1 titanium ester compounds Chemical class 0.000 claims description 9
- JMXKSZRRTHPKDL-UHFFFAOYSA-N titanium ethoxide Chemical group [Ti+4].CC[O-].CC[O-].CC[O-].CC[O-] JMXKSZRRTHPKDL-UHFFFAOYSA-N 0.000 claims description 9
- 239000012046 mixed solvent Substances 0.000 claims description 7
- AYJRCSIUFZENHW-UHFFFAOYSA-L barium carbonate Chemical compound [Ba+2].[O-]C([O-])=O AYJRCSIUFZENHW-UHFFFAOYSA-L 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- 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 claims description 5
- RKTYLMNFRDHKIL-UHFFFAOYSA-N copper;5,10,15,20-tetraphenylporphyrin-22,24-diide Chemical compound [Cu+2].C1=CC(C(=C2C=CC([N-]2)=C(C=2C=CC=CC=2)C=2C=CC(N=2)=C(C=2C=CC=CC=2)C2=CC=C3[N-]2)C=2C=CC=CC=2)=NC1=C3C1=CC=CC=C1 RKTYLMNFRDHKIL-UHFFFAOYSA-N 0.000 claims description 5
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 3
- ITHZDDVSAWDQPZ-UHFFFAOYSA-L barium acetate Chemical compound [Ba+2].CC([O-])=O.CC([O-])=O ITHZDDVSAWDQPZ-UHFFFAOYSA-L 0.000 claims description 3
- WDIHJSXYQDMJHN-UHFFFAOYSA-L barium chloride Chemical compound [Cl-].[Cl-].[Ba+2] WDIHJSXYQDMJHN-UHFFFAOYSA-L 0.000 claims description 3
- 229910001626 barium chloride Inorganic materials 0.000 claims description 3
- RQPZNWPYLFFXCP-UHFFFAOYSA-L barium dihydroxide Chemical compound [OH-].[OH-].[Ba+2] RQPZNWPYLFFXCP-UHFFFAOYSA-L 0.000 claims description 3
- 229910001863 barium hydroxide Inorganic materials 0.000 claims description 3
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 claims description 3
- 238000005286 illumination Methods 0.000 claims description 3
- 239000012535 impurity Substances 0.000 claims description 3
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 claims description 3
- 239000002243 precursor Substances 0.000 claims description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 2
- 238000000926 separation method Methods 0.000 claims description 2
- 239000002086 nanomaterial Substances 0.000 abstract description 14
- 239000002159 nanocrystal Substances 0.000 abstract description 6
- 238000003980 solgel method Methods 0.000 abstract description 4
- 239000002253 acid Substances 0.000 abstract description 2
- 239000003513 alkali Substances 0.000 abstract description 2
- 238000001308 synthesis method Methods 0.000 abstract description 2
- 239000012071 phase Substances 0.000 description 12
- 230000031700 light absorption Effects 0.000 description 4
- 238000003917 TEM image Methods 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 238000005245 sintering Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 125000000896 monocarboxylic acid group Chemical group 0.000 description 2
- 239000002105 nanoparticle Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000010532 solid phase synthesis reaction Methods 0.000 description 2
- 238000000862 absorption spectrum Methods 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- PYWVYCXTNDRMGF-UHFFFAOYSA-N rhodamine B Chemical compound [Cl-].C=12C=CC(=[N+](CC)CC)C=C2OC2=CC(N(CC)CC)=CC=C2C=1C1=CC=CC=C1C(O)=O PYWVYCXTNDRMGF-UHFFFAOYSA-N 0.000 description 1
- 229940043267 rhodamine b Drugs 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
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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
- C01G23/003—Titanates
- C01G23/006—Alkaline earth titanates
-
- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/02—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the alkali- or alkaline earth metals or beryllium
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- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/20—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state
- B01J35/23—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state in a colloidal state
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
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- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
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- C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
- C01P2002/84—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70 by UV- or VIS- data
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- 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
- C01P2004/04—Particle morphology depicted by an image obtained by TEM, STEM, STM or AFM
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/40—Electric properties
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- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
The invention discloses a barium titanate nano cube material and a preparation method and application thereof, and belongs to the technical fields of nano material preparation, solar energy utilization and environmental protection. The invention adopts a sol-gel method, a uniform gel system is obtained by reaction under the condition of mild acid and alkali, and pure-phase barium titanate nano material is obtained by combining a calcination process. The invention solves the problems that the barium titanate material is easy to generate hetero-phase, easy to calcine at high temperature, and coarse in crystal grain, etc. when the traditional synthesis method is adopted to prepare the barium titanate material, the size of the prepared barium titanate nano crystal is smaller than 1 micron, the barium titanate nano crystal presents a cubic morphology, and the barium titanate nano crystal can be used in the fields of photocatalysis purification and gas conversion under the irradiation of sunlight.
Description
Technical Field
The invention relates to the technical fields of nano material preparation, solar energy utilization and environmental protection, in particular to a barium titanate nano cube material and a preparation method and application thereof.
Background
The piezoelectric material can realize the conversion between electric energy and mechanical energy, and has wide application prospect in a plurality of fields. Barium titanate is an important piezoelectric material, and barium titanate with a perovskite phase structure is an ideal material system for researching the piezoelectric effect, but because the barium titanate is composed of metal elements, the barium element and the titanium element have different activities, and the high-temperature sintering can bring about the change of stoichiometric ratio, so that the barium titanate material with small grain size and single phase composition is particularly difficult to obtain.
The common method for preparing barium titanate is a solid-phase sintering method, which adopts oxide as a raw material and other fluxing components are used in an auxiliary way, so that the barium titanate material can be obtained under the high-temperature sintering condition, and the oxide powder is used as the raw material, so that the size of initial grains is greatly restricted, the exchange of material flows is carried out more fully at a higher temperature, the pure-phase barium titanate material with small grain size is difficult to obtain, and the chemical composition of the barium titanate material is difficult to regulate under the atomic scale. In particular, the obtaining of barium titanate materials with a regular shape is often difficult to achieve by solid phase synthesis. Therefore, the method for preparing the pure-phase barium titanate material has important scientific significance and practical significance, and is simple in process and convenient to operate.
Disclosure of Invention
Aiming at the defects existing in the prior art, the invention aims to provide a barium titanate nano cube material, a preparation method and application thereof, wherein a sol-gel method is adopted to react under the condition of mild acid and alkali to obtain a uniform gel system, and then a calcination process is combined to obtain the pure-phase barium titanate nano material. The invention solves the problems that the barium titanate material is easy to generate hetero-phase, easy to calcine at high temperature, and coarse in crystal grain, etc. when the traditional synthesis method is adopted to prepare the barium titanate material, the size of the prepared barium titanate nano crystal is smaller than 1 micron, the barium titanate nano crystal presents a cubic morphology, and the barium titanate nano crystal can be used in the fields of photocatalysis purification and gas conversion under the irradiation of sunlight. The barium titanate nano cube material can be used as a photocatalysis material applied to the field of solar energy utilization, and can be used as a model material for researching the piezoelectricity of barium titanate.
In order to achieve the above purpose, the technical scheme adopted by the invention is as follows:
a barium titanate nano cube material is tetragonal barium titanate crystal, the grain size is smaller than 1 micron, and the barium titanate nano cube material presents the shape of cubes.
The forbidden band width of the nano cubic block material is between 2.8 and 3.4 eV.
The preparation method of the barium titanate nano cube material comprises the following steps:
(1) Preparing a precursor solution: dissolving an ester compound of titanium in glacial acetic acid solution to obtain solution A, and dissolving a barium-containing compound in an alcohol-water mixed solvent to obtain solution B;
(2) Sol-gel reaction: adding the solution B into the solution A, uniformly stirring, firstly preserving heat at 40-80 ℃ for 0.5-3 hours, and then drying at 80-120 ℃ (preferably 85-110 ℃) for 6-24 hours;
(3) Calcining and decomposing: and (3) preserving the heat of the dried product obtained in the step (2) for 2-5 hours at the temperature of 800-1200 ℃ to obtain the barium titanate nano-cube material.
In the step (1), the concentration of the titanium ester compound in the solution A is 0.2-2mol/L, and the titanium ester compound is tetraethyl titanate (ethyl titanate), isopropyl titanate or butyl titanate (tetrabutyl titanate).
In the step (1), the concentration of the barium-containing compound in the solution B is 0.2-2mol/L, and the barium-containing compound is one or more of barium hydroxide, barium acetate, barium carbonate and barium chloride.
In the step (1), the glacial acetic acid solution is formed by mixing glacial acetic acid, alcohol and water, wherein the glacial acetic acid accounts for 10-20% of the total volume, the alcohol accounts for 30-60% of the total volume, and the balance is water; the alcohol-water mixed solvent is prepared from alcohol and water according to the following ratio of 1: (0.5-3) by volume ratio; the alcohol is one or more of ethanol, propanol and butanol.
In the sol-gel reaction process of the step (2), the molar ratio of the barium-containing compound in the solution B to the titanium ester compound in the solution A is 1: (0.5-2).
In the above step (3), the preferable calcination temperature is 850 to 1100 ℃.
The nano cube material has high carrier separation efficiency under the illumination condition, and can be used as a photocatalysis material in the field of environmental purification and gas conversion.
The design idea of the invention is as follows:
the pure-phase barium titanate nano material is difficult to prepare, the product obtained by the solid-phase synthesis method easily contains hetero-phases, and the appearance and morphology of the barium titanate crystal are difficult to control. The invention adopts a mild sol-gel method to limit the grain growth of barium titanate crystals in the calcination process, and can precisely control the stoichiometric ratio of elements at the same time, thereby obtaining the appearance of composite crystal inertial growth and synthesizing the pure-phase barium titanate nano material.
The invention has the advantages that:
1. the invention can control the chemical composition of the barium titanate material to a certain extent by blending the element proportion by a mild sol-gel method.
2. According to the invention, through accurate control of chemical proportion, the barium titanate crystal can perform inertial growth, and the appearance of the cube is obtained. .
3. The invention has simple process flow, simple and convenient operation, low energy consumption and high yield, and is suitable for mass production.
4. The barium titanate material has fine grain size and can be used as an ideal model for researching piezoelectric and multi-field coupling functional ceramics.
Drawings
FIG. 1 is a representation of XRD patterns of crystal structures of nano-scale barium titanate materials prepared in example 1 and example 2;
FIG. 2 is a TEM image of nano-sized barium titanate crystals prepared according to the present invention; wherein: (a) example 1; (b) example 2.
FIG. 3 is an ultraviolet-visible light absorption curve of the nano-sized barium titanate cubic material prepared in example 1.
FIG. 4 is a graph showing the residual amount of RhB versus time for different treatment times under full spectrum excitation for the nano-scale barium titanate cubic material prepared in example 1.
Detailed Description
The invention is described in detail below with reference to the drawings and examples.
In the following embodiments, the titanium ester compound may be tetraethyl titanate (ethyl titanate), isopropyl titanate or butyl titanate (tetrabutyl titanate), and the barium-containing compound may be one or more of barium hydroxide, barium acetate, barium carbonate and barium chloride. The alcohol-water mixed solvent is prepared from ethanol and water according to the following ratio of 1:2, and mixing the materials according to the volume ratio. The concentration of the barium-containing compound in the solution B is 1mol/L.
Example 1
The preparation process of the tetragonal phase barium titanate nanomaterial in this embodiment is as follows:
(1) 5mL of glacial acetic acid (CH) 3 COOH) with 0.01mol of tetrabutyl titanate (C 16 H 36 O 4 Ti) are uniformly mixed. Adding 15mL of ethanol (CH) 3 CH 2 OH) and 10mL of deionized water were added with stirring to obtain solution A, and 0.01mol of Ba (OH) was taken out 2 Dissolving in an alcohol-water mixed solvent to obtain a solution B;
(2) Sol-gel reaction: adding the solution B into the solution A, uniformly stirring, standing at 55 ℃ for 2 hours, and then drying at 100 ℃ for 15 hours;
(3) Calcining and decomposing: and (3) preserving the heat of the product obtained in the step (2) for 3 hours at the temperature of 900 ℃ to obtain the barium titanate nano-cube material (BTO-1).
In fig. 1, BTO-1 is the XRD pattern of the barium titanate nanomaterial prepared in this example, and it can be seen from BTO-1 that the material is pure tetragonal barium titanate crystal without any impurity phase.
Fig. 2 (a) is a TEM image of the barium titanate nanomaterial prepared in this example, and it can be seen from fig. 2 (a) that the prepared barium titanate crystal has uniform size, good dispersibility, and cubic morphology.
Fig. 3 is a graph showing the light absorption spectrum of the barium titanate nanomaterial prepared in example 1, and it can be seen from fig. 3 that the barium titanate nanomaterial exhibits a strong light absorption property in the ultraviolet light absorption region. The band gap is about 3.31eV at the position of-375 nm.
Fig. 4 shows that the barium titanate nano-cube material prepared in this example can decompose organic rhodamine B under the illumination condition.
Example 2
The preparation process of the barium titanate nanomaterial of the embodiment is as follows:
(1) 10mL of glacial acetic acid (CH) 3 COOH) with 0.02mol of tetrabutyl titanate (C 16 H 36 O 4 Ti) are uniformly mixed.30mL of ethanol (CH) was added 3 CH 2 OH) and adding 20mL of deionized water while stirring to obtain solution A, and taking 0.02mol of Ba (OH) 2 Dissolving in an alcohol-water mixed solvent to obtain a solution B;
(2) Sol-gel reaction: adding the solution B into the solution A, uniformly stirring, standing at 60 ℃ for 2 hours, and then drying at 95 ℃ for 20 hours;
(3) Calcining and decomposing: and (3) preserving the heat of the product obtained in the step (2) at the temperature of 1000 ℃ for 3 hours to obtain the barium titanate nano-cube material (BTO-2).
In fig. 1, BTO-2 is the XRD pattern of the barium titanate nanomaterial prepared in this example, and it can be seen from BTO-2 that the material is pure tetragonal barium titanate crystal without any impurity phase.
Fig. 2 (b) is a TEM image of the barium titanate nanomaterial prepared in this example, and it can be seen from fig. 2 (b) that the prepared barium titanate crystal has good dispersibility and a cubic morphology.
Claims (6)
1. A preparation method of a barium titanate nano cube material is characterized by comprising the following steps: the barium titanate nano cube material is tetragonal barium titanate crystals, has no any impurity phase, has a grain size of less than 1 micron, and shows the shape of cubes; the forbidden band width of the nano cubic block material is between 2.8 and 3.4 eV;
the preparation method of the barium titanate nano cube material comprises the following steps:
(1) Preparing a precursor solution: dissolving titanium ester compounds in glacial acetic acid solution to obtain solution A, wherein the concentration of the titanium ester compounds in the solution A is 0.2-2mol/L; dissolving a barium-containing compound in an alcohol-water mixed solvent to obtain a solution B; the concentration of the barium-containing compound in the solution B is 0.2-2mol/L;
(2) Sol-gel reaction: adding the solution B into the solution A, uniformly stirring, firstly preserving heat at the temperature of 40-80 ℃ for 0.5-3 hours, and then drying at the temperature of 80-120 ℃ for 6-24 hours;
(3) Calcining and decomposing: and (3) preserving the heat of the dried product obtained in the step (2) for 2-5 hours at the temperature of 800-1200 ℃ to obtain the barium titanate nano-cube material.
2. The method for preparing the barium titanate nano-cube material according to claim 1, wherein: in the step (1), the ester compound of titanium is tetraethyl titanate (ethyl titanate), isopropyl titanate or butyl titanate (tetrabutyl titanate).
3. The method for preparing the barium titanate nano-cube material according to claim 1, wherein: in the step (1), the barium-containing compound is one or more of barium hydroxide, barium acetate, barium carbonate and barium chloride.
4. The method for preparing the barium titanate nano-cube material according to claim 1, wherein: in the step (1), the glacial acetic acid solution is formed by mixing glacial acetic acid, alcohol and water, wherein the glacial acetic acid accounts for 10-20% of the total volume, the alcohol accounts for 30-60% of the total volume, and the balance is water; the alcohol-water mixed solvent is prepared from alcohol and water according to the following ratio of 1: (0.5-3) by volume ratio; the alcohol is one or more of ethanol, propanol and butanol.
5. The method for preparing the barium titanate nano-cube material according to claim 1, wherein: in the sol-gel reaction process of the step (2), the molar ratio of the barium-containing compound in the solution B to the titanium ester compound in the solution A is 1: (0.5-2).
6. The application of the barium titanate nano-cube material prepared by the preparation method of the barium titanate nano-cube material according to claim 1, which is characterized in that: the nano cube material has high carrier separation efficiency under the illumination condition, and can be used as a photocatalysis material in the field of environmental purification and gas conversion.
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Citations (9)
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|---|---|---|---|---|
| CN1472141A (en) * | 2003-06-30 | 2004-02-04 | 山东省国腾功能陶瓷材料有限公司 | Technology for preparing high-purity nano barium titanate powder |
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