CN106431005B - A kind of strontium titanates-titanium dioxide composite nano tube array film and the preparation method and application thereof - Google Patents
A kind of strontium titanates-titanium dioxide composite nano tube array film and the preparation method and application thereof Download PDFInfo
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- CN106431005B CN106431005B CN201610809678.3A CN201610809678A CN106431005B CN 106431005 B CN106431005 B CN 106431005B CN 201610809678 A CN201610809678 A CN 201610809678A CN 106431005 B CN106431005 B CN 106431005B
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- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title claims abstract description 128
- 239000004408 titanium dioxide Substances 0.000 title claims abstract description 81
- 239000002071 nanotube Substances 0.000 title claims abstract description 60
- 229910052712 strontium Inorganic materials 0.000 title claims abstract description 58
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 title claims abstract description 58
- 239000002131 composite material Substances 0.000 title claims abstract description 52
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 238000006243 chemical reaction Methods 0.000 claims abstract description 93
- 239000011521 glass Substances 0.000 claims abstract description 56
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 44
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 31
- 239000010936 titanium Substances 0.000 claims abstract description 17
- UUCCCPNEFXQJEL-UHFFFAOYSA-L strontium dihydroxide Chemical compound [OH-].[OH-].[Sr+2] UUCCCPNEFXQJEL-UHFFFAOYSA-L 0.000 claims abstract description 15
- 229910001866 strontium hydroxide Inorganic materials 0.000 claims abstract description 15
- 239000002073 nanorod Substances 0.000 claims abstract description 10
- 239000000758 substrate Substances 0.000 claims abstract description 9
- 239000002105 nanoparticle Substances 0.000 claims abstract description 7
- 239000002253 acid Substances 0.000 claims abstract description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 48
- 239000010408 film Substances 0.000 claims description 47
- 239000008367 deionised water Substances 0.000 claims description 42
- 229910021641 deionized water Inorganic materials 0.000 claims description 42
- 229910052573 porcelain Inorganic materials 0.000 claims description 27
- 238000010438 heat treatment Methods 0.000 claims description 21
- 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 15
- 238000001354 calcination Methods 0.000 claims description 14
- 238000003756 stirring Methods 0.000 claims description 14
- 239000010409 thin film Substances 0.000 claims description 13
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 11
- 229910052719 titanium Inorganic materials 0.000 claims description 11
- 238000000034 method Methods 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 6
- 238000012545 processing Methods 0.000 claims description 6
- 150000001875 compounds Chemical class 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 3
- 239000012071 phase Substances 0.000 claims description 3
- 239000007791 liquid phase Substances 0.000 claims description 2
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims 1
- 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 1
- 239000010405 anode material Substances 0.000 abstract description 4
- 238000005530 etching Methods 0.000 abstract description 3
- 229910052788 barium Inorganic materials 0.000 abstract description 2
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 abstract description 2
- 230000015556 catabolic process Effects 0.000 abstract description 2
- 239000003054 catalyst Substances 0.000 abstract description 2
- 238000006731 degradation reaction Methods 0.000 abstract description 2
- 238000011065 in-situ storage Methods 0.000 abstract description 2
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- 231100000252 nontoxic Toxicity 0.000 abstract description 2
- 230000003000 nontoxic effect Effects 0.000 abstract description 2
- 239000005416 organic matter Substances 0.000 abstract 1
- 230000001699 photocatalysis Effects 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 57
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 10
- 230000004044 response Effects 0.000 description 7
- 230000015572 biosynthetic process Effects 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- 239000004065 semiconductor Substances 0.000 description 5
- 238000003786 synthesis reaction Methods 0.000 description 5
- 230000008859 change Effects 0.000 description 4
- 239000000975 dye Substances 0.000 description 4
- 239000000463 material Substances 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 230000005855 radiation Effects 0.000 description 3
- 241000790917 Dioxys <bee> Species 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 238000005286 illumination Methods 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- XONPDZSGENTBNJ-UHFFFAOYSA-N molecular hydrogen;sodium Chemical compound [Na].[H][H] XONPDZSGENTBNJ-UHFFFAOYSA-N 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 239000011591 potassium Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- IATRAKWUXMZMIY-UHFFFAOYSA-N strontium oxide Chemical compound [O-2].[Sr+2] IATRAKWUXMZMIY-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical class CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 1
- 206010070834 Sensitisation Diseases 0.000 description 1
- 229910002370 SrTiO3 Inorganic materials 0.000 description 1
- DQKZBBLOXVFMJQ-UHFFFAOYSA-N [O--].[O--].[Ti+4].[Sr++] Chemical compound [O--].[O--].[Ti+4].[Sr++] DQKZBBLOXVFMJQ-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000002800 charge carrier Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000005352 clarification Methods 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000004042 decolorization Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000005357 flat glass Substances 0.000 description 1
- 230000003760 hair shine Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 238000011017 operating method Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000002957 persistent organic pollutant Substances 0.000 description 1
- 239000011941 photocatalyst Substances 0.000 description 1
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 230000008092 positive effect Effects 0.000 description 1
- 238000006862 quantum yield reaction Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- DCKVNWZUADLDEH-UHFFFAOYSA-N sec-butyl acetate Chemical compound CCC(C)OC(C)=O DCKVNWZUADLDEH-UHFFFAOYSA-N 0.000 description 1
- 230000008313 sensitization Effects 0.000 description 1
- 230000000192 social effect Effects 0.000 description 1
- 239000007784 solid electrolyte Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 1
- 229910001887 tin oxide Inorganic materials 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- -1 two or three Substances 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
- C03C17/34—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions
- C03C17/3411—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions with at least two coatings of inorganic materials
- C03C17/3417—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions with at least two coatings of inorganic materials all coatings being oxide coatings
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
- C03C17/006—Surface treatment of glass, not in the form of fibres or filaments, by coating with materials of composite character
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
- H01G9/20—Light-sensitive devices
- H01G9/2022—Light-sensitive devices characterized by he counter electrode
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C2217/00—Coatings on glass
- C03C2217/40—Coatings comprising at least one inhomogeneous layer
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C2217/00—Coatings on glass
- C03C2217/90—Other aspects of coatings
- C03C2217/94—Transparent conductive oxide layers [TCO] being part of a multilayer coating
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/542—Dye sensitized solar cells
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
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- Power Engineering (AREA)
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- Life Sciences & Earth Sciences (AREA)
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- Crystallography & Structural Chemistry (AREA)
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- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
The present invention relates to a kind of strontium titanates-titanium dioxide composite nano tube array films and the preparation method and application thereof, by three one-step hydrothermals, directly growth is made in electro-conductive glass substrate: first step hydrothermal synthesis titanium dioxide nano-rod, second step hydro-thermal performs etching generation titania nanotube to it, third step hydro-thermal reaction is using strontium hydroxide as barium source, the final laminated film for obtaining Ca-Ti ore type metatitanic acid strontium nanoparticle and being uniformly distributed in Nano tube array of titanium dioxide surface, wherein titania nanotube is vertically arranged in electro-conductive glass substrate.The laminated film may be used as the anode material of solar battery, or the degradation treatment of photocatalytic water or organic matter is carried out as photochemical catalyst.The present invention uses three one-step hydrothermal fabricated in situ, and preparation process and required equipment are simple, and controllability is strong, production safety, nontoxic, environmentally friendly；It is assembled into the capturing ability that light anode can be improved to sunlight in solar battery, improves incident photon-to-electron conversion efficiency.
Description
Technical field:
The present invention relates to a kind of strontium titanates-titanium dioxide composite nano tube array film of special microscopic appearance structure and its
Preparation method and application, belong to semiconductor nanometer composite material preparation technical field, be applicable to solar battery light anode or
Photocatalyst for degrading dye wastewater.
Background technique:
With the continuous upgrading of energy and environmental problem, people are also growing to the demand of new energy.Solar energy
It as the huge green energy resource of reserves, its utilization and is converted to for popular research field, novel environmental close friend's semiconductor is multiple
Condensation material meets the development of current era, and is concerned, and develops and uses environmental-friendly semiconductor composite for the mankind
Sustainable development have important economy and social effect, while being also the research work with great challenge.
Titanium dioxide can effectively convert solar energy into electric energy or chemical energy, have and clean, is mild, efficiently, surely
The advantages that determining.In order to overcome, titanium dioxide forbidden bandwidth is big, charge is excited to be easy the deficiencies of compound, it is necessary to solve two technology difficulties
Topic: (1) forbidden bandwidth (~3.2eV) of titanium dioxide determines that it can only be excited by the ultraviolet light less than 380nm, and is less than
This portion of energy of the ultraviolet light of 380nm only accounts for 5% or so up to earth surface solar radiation, it is therefore desirable to widen titanium dioxide
To the response range of spectrum, the utilization rate of solar energy especially visible region is improved；(2) quick between charge carrier compound causes
Quantum yield is normally no higher than 20%, this allow for solar energy practical efficiency only have about 1%, so improve light induced electron and
Efficiently separating, inhibiting compound for hole pair is also the necessary means for improving titanium dioxide photoelectric transformation efficiency.In titanium dioxide table
Face deposition perovskite is a kind of effective ways for improving photo-quantum efficiency.Strontium titanates (SrTiO3) it is a kind of typical perovskite knot
Structure semiconductor, forbidden bandwidth 3.2eV are the another kind of semiconductors with larger application potential in addition to the titanium
Photoelectric material can be well matched with titanium dioxide.
Summary of the invention:
Present invention aims to overcome that disadvantage of the existing technology, provides a kind of strontium titanates-titanium dioxide composite Nano
Pipe array film and the preparation method and application thereof.
In order to achieve the above-mentioned object of the invention, a kind of strontium titanates of the invention-titanium dioxide composite nano tube array film,
Be characterized in that strontium titanates-titanium dioxide composite nano tube is aligned in high-sequential, bore average-size be 40~
100nm, pipe range are 1~2 μm, and strontium titanates nanoparticle is evenly distributed on the surface of nanotube, and crystalline phase is Ca-Ti ore type, size
For 1~100nm.
Titanium dioxide in the strontium titanates-titanium dioxide composite nano tube array film belongs to rutile-type.
A kind of preparation method of strontium titanates-titanium dioxide composite nano tube array film, using three one-step hydrothermals in conduction
Directly growth is made in substrate of glass, operates in accordance with the following steps:
The hydrochloric acid that deionized water and concentration are 36%-38% according to volume ratio is at room temperature to mix at 1: 6-6: 1 by the first step
30mL is taken after uniformly, and 0.1-1mL titanium source presoma is added, stirs evenly to obtain transparent clear solution, pours into and be placed with inclined conduction
In the reaction kettle of sheet glass, the conductive of electro-conductive glass is put into baking oven downwards and carries out hydro-thermal reaction, and heating temperature is 80~
240 DEG C, heating time is 1~12 hour, and to which after completion of the reaction, reaction kettle is taken out, cooled to room temperature takes out conductive glass
Glass is rinsed well with deionized water, stand-by after dry；The titanium source presoma is titanium tetrachloride, tetrabutyl titanate, four isopropanols
One of titanium, two or three, liquid phase；
Electro-conductive glass piece inclination made from step 1 with titanium dioxide nanorod array film is put into anti-by second step
Answer in kettle, it is conductive downwards, according to volume ratio be at room temperature 1: 6~6: 1 by the hydrochloric acid that deionized water and concentration are 36%-38%
30mL is taken after mixing, pours into reaction kettle, places into baking oven heating, carries out hydro-thermal reaction, heating temperature is 80~240 DEG C,
Heating time is 0.5~12 hour, and to which after completion of the reaction, reaction kettle is taken out, cooled to room temperature takes out electro-conductive glass,
It is rinsed well with deionized water, it is stand-by after dry；
Third step, by the electro-conductive glass piece made from step 2 with titanium dioxide nano-pipe array thin film with titanium dioxide
Nano-pipe array thin film tilts be put into reaction kettle downwards, then 30mL10-7~10-2The strontium hydroxide solution of mol/L is put into
In reaction kettle, adjustment pH value range is 8-14, places into baking oven heating, carries out hydro-thermal reaction, and heating temperature is 100~240 DEG C,
Heating time is 1~24 hour, after completion of the reaction, reaction kettle is taken out, cooled to room temperature, takes out electro-conductive glass, is used in combination
Deionized water is washed repeatedly to the reactionless object residual in its surface, is spontaneously dried at room temperature；
4th step, by made from step 3 with strontium titanates-titanium dioxide composite nano tube array film electro-conductive glass
Piece, which is transferred in porcelain boat and porcelain boat is put into high temperature furnace, carries out calcination processing, calcination temperature be 300~600 DEG C, the time be 1~
12 hours；
5th step takes out porcelain boat, obtaining to surface has Ca-Ti ore type metatitanic acid strontium to after the reaction was completed, cool to room temperature with the furnace
The titanium dioxide composite nano tube array film of nano particle load.
Strontium titanates of the invention-titanium dioxide composite nano tube array film application, under solar simulating radiation illumination
Decolorization of dye effluent degradation can carry out the assembling of solar battery as anode material, or be used for light as photochemical catalyst
Solve the photocatalytic degradation of water hydrogen manufacturing and organic pollutant.
Compared with prior art, the advantages and positive effects of the present invention are: 1, synthesis strontium titanates-titanium dioxide composite Nano
The low toxicity or nontoxic of reagent needed for pipe array film, synthesis process is mild, environmentally friendly；2, titanium dioxide nano-pipe array thin film
In preparation process, reaction temperature is simple with time adjusting method, has efficiently controlled the shape size of titania nanotube；3,
The change of strontium hydroxide concentration has effectively regulated and controled the uniformity of metatitanic acid strontium particle；4, in product calcination process, temperature and time
Modification scope is wide, simple to operation；5, the large specific surface area of the titanium dioxide of nano tube structure, conducive to the deposition of strontium titanates；6,
Using three one-step hydrothermal fabricated in situ, has many advantages, such as simple and easy to control, highly selective, high yield, saves the energy, meet current society
The requirement of meeting green chemistry.It is assembled into the capturing ability that light anode can be improved to sunlight in solar battery, improves light
Electrotransformation efficiency.
Detailed description of the invention:
Fig. 1 is strontium titanates-titanium dioxide composite nano tube array film titanium dioxide nano-rod, dioxy in the synthesis process
Change titanium nanotube, strontium titanates-titanium dioxide composite nano tube structural schematic diagram；
Fig. 2 is strontium titanates-titanium dioxide composite nano tube array film scanning electron microscopic picture；
Fig. 3 is strontium titanates-titanium dioxide composite nano tube array film of different strontium hydroxide solution concentration synthesis in mould
Current -voltage curve under quasi- sunlight irradiation.
Specific embodiment:
The present invention is further elaborated in the following with reference to the drawings and specific embodiments.
Embodiment 1,
Using tetrabutyl titanate as titanium source presoma, concentrated hydrochloric acid is etching agent, and strontium hydroxide solution is that barium source passes through hydro-thermal method
Strontium titanates-titanium dioxide composite nano tube array film is prepared, operating procedure is as follows:
(1), by concentration be 36.5% hydrochloric acid and deionized water be respectively 1:6,1:4,1:2,1:1,2 according to volume ratio:
Isosorbide-5-Nitrae: 1,6: 1 ratio prepares the mixed solution of 30mL, and after magnetic stirrer 5min, 0.6mL metatitanic acid is being added just thereto
Butyl ester obtains transparent clear solution, as reaction solution, for use after stirring 15min；
(2), a piece of FTO (fluorine-doped tin oxide) electro-conductive glass is taken, inclination is put into autoclave, and conduction downwards, will
Reaction solution pours into autoclave, 150 DEG C of hydro-thermal reaction 4h in baking oven is put into, to which after completion of the reaction, autoclave is taken
Out, cooled to room temperature is taken out FTO electro-conductive glass, is rinsed well with deionized water, stand-by after dry；
(3), it after 5min being mixed in 36.5% concentrated hydrochloric acid of 15mL and 15mL deionized water at room temperature, is waited for for reaction solution
With, take a piece of with titanic oxide nanorod array FTO electro-conductive glass, inclination is put into autoclave, it is conductive downwards, will
Reaction solution pours into autoclave, places into baking oven heating, and 150 DEG C of hydro-thermal reaction 2.5h are anti-by high pressure to after completion of the reaction
Kettle is answered to take out, cooled to room temperature is taken out FTO electro-conductive glass, rinsed well with deionized water, stand-by after dry；
(4), measuring 30mL concentration is 10-5The strontium hydroxide clear solution of mol/L, then with sodium hydroxide or hydrogen-oxygen
Changing potassium solution to adjust pH value is 12, gives over to reaction solution, for use；
(5), by the FTO glass with titanium dioxide nano-pipe array thin film, with titanium dioxide nano-pipe array thin film face
It tilts down and is put into autoclave, pour into above-mentioned reaction solution, be put into 150 DEG C reaction 12 hours in baking oven, after completion of the reaction,
Autoclave is taken out, cooled to room temperature, takes out electro-conductive glass, and washed repeatedly to its surface without anti-with deionized water
It answers object to remain, spontaneously dries at room temperature；
(6), it will be transferred in porcelain boat with strontium titanates-titanium dioxide composite nano tube array film FTO electro-conductive glass piece
And porcelain boat is put into high temperature furnace and is carried out calcination processing 3 hours, calcination temperature is 450 DEG C；
(7), it after reaction, cools to room temperature with the furnace, takes out porcelain boat, obtain when first step hydro-thermal reaction in reaction substrate
Strontium titanates-titanium dioxide composite nano tube array film of concentrated hydrochloric acid and the preparation of deionized water different proportion, and be kept in dark place.
Strontium titanates-titanium dioxide composite nano tube array film titanium dioxide nano-rod, titanium dioxide in the synthesis process
Nanotube, strontium titanates-titanium dioxide composite nano tube structure are as shown in Figure 1, A is rodlike titanium dioxide nano-rod, figure in Fig. 1
B is the titania nanotube for the tubular structure that titanium dioxide nano-rod obtains after concentrated hydrochloric acid etches in 1, and C is to be added in Fig. 1
Strontium titanates-titanium dioxide the composite nano tube obtained after strontium hydroxide solution reaction.Wherein, 1 is FTO electro-conductive glass, and 2 be metatitanic acid
Strontium nanoparticle.From A to B, arrow indicates etching process, and from B to C, arrow indicates that the reaction process after strontium hydroxide solution is added.
Strontium titanates made from the method for the present invention-titanium dioxide composite nano tube array film scanning electron microscopic picture such as Fig. 2 institute
Show.
Strontium titanates-titanium dioxide composite nano tube is aligned in high-sequential, bore average-size be 40~
100nm, pipe range are 1~2 μm, and strontium titanates nanoparticle is evenly distributed on the surface of nanotube, and crystalline phase is Ca-Ti ore type, size
For 1~100nm.Titanium dioxide in strontium titanates-titanium dioxide composite nano tube array film belongs to rutile-type.
Embodiment 2,
(1), by after 36.5% concentrated hydrochloric acid of 15mL and 15mL deionized water magnetic stirrer 5min, distinguish thereto
0.1mL, 0.2mL, 0.4mL, 0.6mL, 0.8mL is added, the tetrabutyl titanate of 1.0mL obtains transparent clarification after stirring 15min
Solution, as reaction solution, for use；
Step (2)~(6) are the same as embodiment 1；
(7), it after reaction, cools to room temperature with the furnace, takes out porcelain boat, obtain when first step hydro-thermal reaction in reaction substrate
Strontium titanates-titanium dioxide composite nano tube array film of different tetrabutyl titanate usage amount preparations, and be kept in dark place.
Embodiment 3,
(1), it by after 36.5% concentrated hydrochloric acid of 15mL and 15mL deionized water magnetic stirrer 5min, is added thereto
0.6mL tetrabutyl titanate obtains transparent clear solution, as reaction solution, for use after stirring 15min；
(2), a piece of FTO electro-conductive glass is taken, inclination is put into autoclave, and conduction all turns downwards, by reaction solution
Enter in autoclave, is put into baking oven the hydro-thermal reaction 4 at 80 DEG C, 120 DEG C, 150 DEG C, 180 DEG C, 210 DEG C, 240 DEG C respectively
Hour, to which after completion of the reaction, autoclave is taken out, cooled to room temperature takes out FTO electro-conductive glass, uses deionized water
It rinses well, drying is stand-by；
Step (3)~(6) are the same as embodiment 1；
(7), it after reaction, cools to room temperature with the furnace, takes out porcelain boat, obtain differential responses temperature when first step hydro-thermal reaction
The strontium titanates prepared under the conditions of degree-titanium dioxide composite nano tube array film, and be kept in dark place.
Embodiment 4,
(1), it by after 36.5% concentrated hydrochloric acid of 15mL and 15mL deionized water magnetic stirrer 5min, is added thereto
0.6mL tetrabutyl titanate obtains transparent clear solution, as reaction solution, for use after stirring 15min；
(2), a piece of FTO electro-conductive glass is taken, inclination is put into autoclave, and conduction all turns downwards, by reaction solution
Enter in autoclave, be put into baking oven 150 DEG C hydro-thermal reaction 1~12 hour, to which after completion of the reaction, autoclave is taken
Out, cooled to room temperature is taken out FTO electro-conductive glass, is rinsed well with deionized water, and drying is stand-by；
Step (3)~(6) are the same as embodiment 1；
(7), it after reaction, cools to room temperature with the furnace, porcelain boat is taken out, when obtaining differential responses when first step hydro-thermal reaction
Between under the conditions of strontium titanates-titanium dioxide composite nano tube array film for preparing, and be kept in dark place.
Embodiment 5,
(1), it by after 36.5% concentrated hydrochloric acid of 15mL and 15mL deionized water magnetic stirrer 5min, is added thereto
0.6mL tetrabutyl titanate obtains transparent clear solution, as reaction solution, for use after stirring 15min；
(2), a piece of FTO electro-conductive glass is taken, inclination is put into autoclave, and reaction solution downwards, is poured into height by conduction
It presses in reaction kettle, is put into 150 DEG C of hydro-thermal reaction 4h in baking oven and is naturally cooled to which after completion of the reaction, autoclave is taken out
Room temperature is taken out FTO electro-conductive glass, is rinsed well with deionized water, stand-by after dry；
(3), by 36.5% concentrated hydrochloric acid and deionized water respectively according to volume ratio be 1: 6,1: 4,1: 2,1: 1,2:1,4: 1,6
: 1 ratio prepares the mixed solution of 30mL, takes a piece of with dioxy for use after magnetic stirrer 5min as reaction solution
Change titanium nanometer stick array FTO electro-conductive glass, inclination is put into autoclave, and reaction solution downwards, it is anti-to be poured into high pressure by conduction
Answer in kettle, place into baking oven heating, 150 DEG C hydro-thermal reaction 2.5 hours, it is natural to which after completion of the reaction, autoclave is taken out
It is cooled to room temperature, takes out FTO electro-conductive glass, rinsed well with deionized water, drying is stand-by；
(4), measuring 30mL concentration is 10-5The strontium hydroxide clear solution of mol/L, then with sodium hydroxide or hydrogen-oxygen
Changing potassium solution to adjust pH value is 12, gives over to reaction solution, for use；
(5), by the FTO glass with titanium dioxide nano-pipe array thin film, with titanium dioxide nano-pipe array thin film face
It tilts down and is put into autoclave, pour into above-mentioned reaction solution, be put into 150 DEG C reaction 12 hours in baking oven, after completion of the reaction,
Autoclave is taken out, cooled to room temperature, takes out electro-conductive glass, and washed repeatedly to its surface without anti-with deionized water
It answers object to remain, spontaneously dries at room temperature；
(6), it will be transferred in porcelain boat with strontium titanates-titanium dioxide composite nano tube array film FTO electro-conductive glass piece
And porcelain boat is put into high temperature furnace and is carried out calcination processing 3 hours, calcination temperature is 450 DEG C；
(7), it after reaction, cools to room temperature with the furnace, takes out porcelain boat, obtain when second step hydro-thermal reaction in reaction substrate
Strontium titanates-titanium dioxide composite nano tube array film of concentrated hydrochloric acid and the preparation of deionized water different proportion, and be kept in dark place.
Embodiment 6,
(1), it by after 36.5% concentrated hydrochloric acid of 15mL and 15mL deionized water magnetic stirrer 5min, is added thereto
0.6mL tetrabutyl titanate obtains transparent clear solution, as reaction solution, for use after stirring 15min；
(2), a piece of FTO electro-conductive glass is taken, inclination is put into autoclave, and reaction solution downwards, is poured into height by conduction
It presses in reaction kettle, is put into 150 DEG C of hydro-thermal reaction 4h in baking oven and is naturally cooled to which after completion of the reaction, autoclave is taken out
Room temperature is taken out FTO electro-conductive glass, is rinsed well with deionized water, stand-by after dry；
(3) after 5min being mixed in 36.5% concentrated hydrochloric acid of 15mL and 15mL deionized water, as reaction solution, for use；It takes
A piece of to tilt and be put into autoclave with titanic oxide nanorod array FTO electro-conductive glass, conduction downwards, will react
Liquid pours into autoclave, baking oven heating is placed into, respectively at 80 DEG C, 120 DEG C, 150 DEG C, 180 DEG C, 210 DEG C, 240 DEG C
Hydro-thermal reaction 2.5 hours, to which after completion of the reaction, autoclave is taken out, cooled to room temperature took out FTO electro-conductive glass,
It is rinsed well with deionized water, drying is stand-by；
Step (4)~(6) are the same as embodiment 1；
(7), it after reaction, cools to room temperature with the furnace, takes out porcelain boat, obtain different temperatures item when second step hydro-thermal reaction
The strontium titanates prepared under part-titanium dioxide composite nano tube array film, and be kept in dark place.
Embodiment 7,
(1), it by after 36.5% concentrated hydrochloric acid of 15mL and 15mL deionized water magnetic stirrer 5min, is added thereto
0.6mL tetrabutyl titanate obtains transparent clear solution, as reaction solution, for use after stirring 15min；
(2), a piece of FTO electro-conductive glass is taken, inclination is put into autoclave, and reaction solution downwards, is poured into height by conduction
It presses in reaction kettle, is put into 150 DEG C of hydro-thermal reaction 4h in baking oven and is naturally cooled to which after completion of the reaction, autoclave is taken out
Room temperature is taken out FTO electro-conductive glass, is rinsed well with deionized water, stand-by after dry；
(3) after 5min being mixed in 36.5% concentrated hydrochloric acid of 15mL and 15mL deionized water, as reaction solution, for use；It takes
A piece of to tilt and be put into autoclave with titanic oxide nanorod array FTO electro-conductive glass, conduction downwards, will react
Liquid pours into autoclave, places into baking oven heating, 150 DEG C hydro-thermal reaction 0.5~12 hour, will be high to after completion of the reaction
Reaction kettle is pressed to take out, cooled to room temperature is taken out FTO electro-conductive glass, rinsed well with deionized water, and drying is stand-by；
Step (4)~(6) are the same as embodiment 1；
(7), it after reaction, cools to room temperature with the furnace, takes out porcelain boat, obtain different time item when second step hydro-thermal reaction
The strontium titanates prepared under part-titanium dioxide composite nano tube array film, and be kept in dark place.
Embodiment 8,
(1), it by after 36.5% concentrated hydrochloric acid of 15mL and 15mL deionized water magnetic stirrer 5min, is added thereto
0.6mL tetrabutyl titanate obtains transparent clear solution, as reaction solution, for use after stirring 15min；
Step (2)~(4) are the same as embodiment 1；
(5), by the FTO glass with titanium dioxide nano-pipe array thin film, with titanium dioxide nano-pipe array thin film face
It tilts down and is put into autoclave, pour into the reaction solution in step (4), be put into baking oven respectively at 100 DEG C, 120 DEG C,
140 DEG C, 160 DEG C, 180 DEG C, 200 DEG C, 220 DEG C, 240 DEG C are heated 12 hours, and after completion of the reaction, autoclave is taken out, from
It is so cooled to room temperature, takes out electro-conductive glass, and washed repeatedly with deionized water to the reactionless object residual in its surface, it is natural at room temperature
It is dry；
(6), it will be transferred in porcelain boat with strontium titanates-titanium dioxide composite nano tube array film FTO electro-conductive glass piece
And porcelain boat is put into high temperature furnace and is carried out calcination processing 3 hours, calcination temperature is 450 DEG C；
(7), it after reaction, cools to room temperature with the furnace, takes out porcelain boat, obtain differential responses temperature when third step hydro-thermal reaction
The strontium titanates prepared under the conditions of degree-titanium dioxide composite nano tube array film, and be kept in dark place.
Embodiment 9,
(1), it by after 36.5% concentrated hydrochloric acid of 15mL and 15mL deionized water magnetic stirrer 5min, is added thereto
0.6mL tetrabutyl titanate obtains transparent clear solution, as reaction solution, for use after stirring 15min；
Step (2)~(4) are the same as embodiment 1；
(5), by the FTO glass with titanium dioxide nano-pipe array thin film, with titanium dioxide nano-pipe array thin film face
It tilts down and is put into autoclave, pour into the reaction solution in step (4), be put into 150 DEG C heating 1-24 hours in baking oven, instead
After answering, autoclave is taken out, cooled to room temperature, takes out electro-conductive glass, and washed repeatedly with deionized water to
The reactionless object residual in its surface, spontaneously dries at room temperature；
(6), it will be transferred in porcelain boat with strontium titanates-titanium dioxide composite nano tube array film FTO electro-conductive glass piece
And porcelain boat is put into high temperature furnace and is carried out calcination processing 3 hours, calcination temperature is 450 DEG C；
(7), it after reaction, cools to room temperature with the furnace, porcelain boat is taken out, when obtaining differential responses when third step hydro-thermal reaction
Between under the conditions of strontium titanates-titanium dioxide composite nano tube array film for preparing, and be kept in dark place.
Embodiment 10,
(1), it by after 36.5% concentrated hydrochloric acid of 15mL and 15mL deionized water magnetic stirrer 5min, is added thereto
0.6mL tetrabutyl titanate obtains transparent clear solution, as reaction solution, for use after stirring 15min；
Step (2)~(3) are the same as embodiment 1；
(4), the strontium hydroxide (10 of 30mL various concentration is measured respectively-2-10-7Mol/L then) clear solution uses hydrogen-oxygen
Changing sodium or potassium hydroxide solution adjusting pH value is 12, gives over to reaction solution, for use；
Step (5)~(6) are the same as embodiment 1；
(7), it after reaction, is cooled to room temperature, obtains the hydrogen of various concentration in reaction substrate when third step hydro-thermal reaction
Strontium titanates-titanium dioxide composite nano tube array film of strontium oxide strontia solution preparation, and be kept in dark place.
Embodiment 11,
(1), it by after 36.5% concentrated hydrochloric acid of 15mL and 15mL deionized water magnetic stirrer 5min, is added thereto
0.6mL tetrabutyl titanate obtains transparent clear solution, as reaction solution, for use after stirring 15min；
Step (2)~(3) are the same as embodiment 1；
(4), measuring concentration in 30mL above-mentioned steps is 10-5The strontium hydroxide clear solution of mol/L, then uses hydroxide
It is respectively 8,9,10,11,12,13,14 that sodium or potassium hydroxide solution, which adjust the solution ph, for use；
Step (5)~(6) are the same as embodiment 1；
(7), it after reaction, cools to room temperature with the furnace, takes out porcelain boat, obtain when third step hydro-thermal reaction in reaction substrate
The strontium titanates prepared under different pH values-titanium dioxide composite nano tube array film, and be kept in dark place.
Embodiment 12,
(1), it by after 36.5% concentrated hydrochloric acid of 15mL and 15mL deionized water magnetic stirrer 5min, is added thereto
0.6mL tetrabutyl titanate obtains transparent clear solution, as reaction solution, for use after stirring 15min；
Step (2)~(5) are the same as embodiment 1；
(6), it will be transferred to porcelain boat with strontium titanates-titanium dioxide composite nano tube array film FTO electro-conductive glass and incite somebody to action
Porcelain boat is put into Muffle furnace, is calcined 3 hours at 300 DEG C, 350 DEG C, 400 DEG C, 450 DEG C, 500 DEG C, 550 DEG C, 600 DEG C respectively；
(7), it after reaction, cools to room temperature with the furnace, takes out porcelain boat, obtain the titanium prepared under the conditions of different calcination temperatures
Sour strontium-titanium dioxide composite nano tube array film, and be kept in dark place.
Embodiment 13,
The present invention also provides the strontium titanates of above-mentioned preparation-titanium dioxide composite nano tube array film purposes, are used as dye
Expect sensitization solar battery anode material, there is photoelectric current generation under the irradiation of analog light source.Light source is that intensity is 100mW/cm2
Xenon lamp (150W, Newport 96000), wherein conductive with strontium titanates-titanium dioxide composite nano tube array film FTO
Glass is working electrode, and platinum plating FTO electro-conductive glass is made to use CsSnI to electrode2.95F0.05Make solid electrolyte, dyestuff is
N719 is tested under room temperature.Incident light shines perpendicular to light anode, illuminating area 0.50cm2, current -voltage curve test is in electrification
It learns and is carried out on work station (Shanghai Chen Hua instrument company, CHI760D).
Using strontium titanates-titanium dioxide composite nano tube array film prepared by embodiment 10 as solar battery anode material
Material is investigated under solar simulating radiation illumination, and in third step hydro-thermal reaction, difference strontium hydroxide concentration prepares strontium titanates-dioxy
Change the photocurrent response situation of titanium composite nano tube array film.As shown in Fig. 3, what is synthesized under different strontium hydroxide concentration should
Laminated film has photocurrent response, illustrates the characteristic that there is the laminated film luminous energy to convert to electric energy.As strontium hydroxide is molten
The continuous improvement of liquid concentration, density of photocurrent have the tendency that first becoming larger, become smaller again.
Claims (2)
1. a kind of strontium titanates-titanium dioxide composite nano tube array film preparation method, it is characterised in that use three step hydro-thermals
Directly growth is made method in electro-conductive glass substrate, operates in accordance with the following steps: the first step, at room temperature by deionized water and concentration
According to volume ratio it is that 1:6-6:1 takes 30mL after mixing for the hydrochloric acid of 36%-38%, 0.1-1mL titanium source presoma is added, stirs
Mix uniform transparent clear solution, pour into the reaction kettle for being placed with inclined electro-conductive glass piece, electro-conductive glass it is conductive downwards,
It being put into baking oven and carries out hydro-thermal reaction, heating temperature is 80~240 DEG C, and heating time is 1~12 hour, to after completion of the reaction,
Reaction kettle is taken out, cooled to room temperature, takes out electro-conductive glass, rinsed well with deionized water, it is stand-by after dry；The titanium
Source presoma is one of titanium tetrachloride, tetrabutyl titanate, titanium tetraisopropylate, two or three, liquid phase；Second step will walk
The rapid one electro-conductive glass piece inclination with titanium dioxide nanorod array film obtained is put into reaction kettle, it is conductive downwards,
It according to volume ratio is at room temperature that 1:6~6:1 takes 30mL after mixing by the hydrochloric acid that deionized water and concentration are 36%-38%,
Reaction kettle is poured into, baking oven heating is placed into, carries out hydro-thermal reaction, heating temperature is 80~240 DEG C, and heating time is 0.5~12
Hour, to which after completion of the reaction, reaction kettle is taken out, cooled to room temperature takes out electro-conductive glass, is rinsed with deionized water dry
Only, stand-by after drying；Third step, by the electro-conductive glass piece made from step 2 with titanium dioxide nano-pipe array thin film with two
Titania nanotube array film tilts be put into reaction kettle downwards, then 30mL10-7~10-2The strontium hydroxide of mol/L is molten
Liquid is put into reaction kettle, adjustment pH value range be 8-14, place into baking oven heating, carry out hydro-thermal reaction, heating temperature be 100~
240 DEG C, heating time is 1~24 hour, after completion of the reaction, reaction kettle is taken out, cooled to room temperature, takes out conductive glass
Glass, and washed repeatedly with deionized water to the reactionless object residual in its surface, it spontaneously dries at room temperature；4th step, by step 3 system
What is obtained is transferred in porcelain boat with strontium titanates-titanium dioxide composite nano tube array film electro-conductive glass piece and is put into porcelain boat
Calcination processing is carried out in high temperature furnace, calcination temperature is 300~600 DEG C, and the time is 1~12 hour；5th step is completed wait react
Afterwards, it cools to room temperature with the furnace, takes out porcelain boat, it is compound to obtain the titanium dioxide for having Ca-Ti ore type metatitanic acid strontium nano particle to load to surface
Nano-pipe array thin film.
2. a kind of strontium titanates according to claim 1-titanium dioxide composite nano tube array film preparation method, special
Sign be that strontium titanates obtained-titanium dioxide composite nano tube is aligned in high-sequential, bore average-size be 40~
100nm, pipe range are 1~2 μm, and strontium titanates nanoparticle is evenly distributed on the surface of nanotube, and crystalline phase is Ca-Ti ore type, size
For 1~100nm；Titanium dioxide in the strontium titanates-titanium dioxide composite nano tube array film belongs to rutile-type.
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