CN101949054B - Method for preparing single-crystal anatase titanium dioxide film - Google Patents
Method for preparing single-crystal anatase titanium dioxide film Download PDFInfo
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- CN101949054B CN101949054B CN 201010256109 CN201010256109A CN101949054B CN 101949054 B CN101949054 B CN 101949054B CN 201010256109 CN201010256109 CN 201010256109 CN 201010256109 A CN201010256109 A CN 201010256109A CN 101949054 B CN101949054 B CN 101949054B
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Abstract
The invention discloses a method for preparing a single-crystal anatase titanium dioxide film, which comprises the following steps of: washing a titanium metal plate with thickness of over 1 millimeter by using acid washing solution prepared from hydrofluoric acid, nitric acid and deionized water, then ultrasonically cleaning the titanium metal plate by using deionized water, putting the titanium metal plate into a polytetrafluoroethylene hydrothermal tank and soaking the titanium metal plate into aqueous solution of hydrogen fluoride, performing hydrothermal reaction for 3 to 12 hours at 180 DEG C, cleaning the titanium metal plate by using the deionized water, and drying the titanium metal plate. The method in which direct reaction of the titanium metal plate and the aqueous solution of the hydrogen fluoride is simple and feasible, needs no a template agent or a catalyst, and needs no subsequent treatment. The prepared single-crystal anatase titanium dioxide film has strong adhesive force, good quality and anatase {001} high-energy crystal face of high photocatalysis activity, and can be widely applied in the fields of photocatalysis and gas sensors, thin film solar cells and the like.
Description
Technical field
The present invention relates to a kind of preparation method of monocrystalline anatase titania film, the metal nanometer material technical field.
Background technology
Different nanostructures is to the performance performance important influence of titanium oxide in numerous Application Areass such as photochemical catalysis, photoelectrocatalysis, gas sensor, thin-film solar cells, lithium ion battery and electrochromism.So far; People have synthesized the titanium oxide of variforms such as nanotube, nano wire, nanometer rod, nanometer band, nanometer flower, hollow Nano microballoon, polycrystalline face microballoon, and the different nanostructure of these patterns has all shown the physical chemistry and the photoelectric properties of different separately excellences.
In the common three kinds of crystalline structure of titanium oxide, with respect to rutile and brookite, anatase octahedrite has best photocatalysis performance.Existing result of study shows simultaneously, with respect to the most stable the 110} crystal face, and the anatase octahedrite phase { 001} crystal face energy is higher, also has higher photocatalytic activity.Therefore, { synthesizing of the anatase octahedrite of 001} crystal face attracted domestic and international many investigators' attention to have height ratio.2008, people such as Australian Yang adopted TiF
4With HF solution, under hydrothermal condition, taken the lead in synthesizing and have height ratio { the anatase single crystal powder of 001} crystal face, the gained monocrystalline is for having high symmetric rescinded angle octahedral structure.Because F
-Ion is in that { this crystal face has been stablized in the selective adsorption on the 001} crystal face, makes that unsettled relatively on the thermodynamics { a large amount of existence of 001} crystal face become possibility.But, TiF
4Cost an arm and a leg, and suction decomposition easily in air, poor stability is difficult to handle.2010, people such as the Liu of the Chinese Academy of Sciences placed H with the metal titanium powder
2O
2In+HF the hydrothermal system, also obtained the anatase single crystal powder of similar structures.
In practical applications such as photocatalysis sewage processing, for fear of follow-up loaded down with trivial details catalyst fines removal process, often need titania powder is immobilized on substrate.This can realize to scrape slurry agglomerating technology through titania powder is processed slurry.Predictably, the titanium dioxide film that reaction in forms on particular substrate will have even more ideal bonding force, and can omit intermediary and scrape the slurry sintering step.
Summary of the invention
The purpose of this invention is to provide the height ratio that a kind of process is simple, cost the is low { preparation method of 001} crystal face monocrystalline anatase titania film.
The preparation method of monocrystalline anatase titania film of the present invention may further comprise the steps:
1) be that 50～55% hydrofluoric acid, mass concentration are that 65～68% nitric acid mixed with deionized water in 1: 3: 6 by volume with mass concentration, pickle solution;
2) the preparation mass concentration is 0.15～0.80% aqueous hydrogen fluoride solution, inserts in the tetrafluoroethylene hydro-thermal jar, and the volume ratio of aqueous hydrogen fluoride solution and hydro-thermal jar is 4: 5;
3) thickness is the pickle solution pickling of metallic titanium plate with step 1) more than 1 millimeter after; Use the deionized water ultrasonic cleaning clean again; Put into tetrafluoroethylene hydro-thermal jar and be immersed in aqueous hydrogen fluoride solution,, use washed with de-ionized water 180 ℃ of following hydro-thermal reactions 3～12 hours; Drying obtains attached to the monocrystalline anatase titania film on the metallic titanium plate.
The monocrystalline anatase titania film that the inventive method makes, about 100 microns of thickness is made up of the octahedra monocrystalline of the rescinded angle of big or small approximate number micron, and two parallel surfaces are anatase octahedrite { the 001} high energy crystal face with highlight catalytic active up and down.
The present invention adopts metallic titanium plate and aqueous hydrogen fluoride solution direct reaction, and method is simple, do not need template and catalyzer, do not need subsequent heat treatment.The monocrystalline anatase titania film strong adhesion that makes, quality is good, has anatase octahedrite { the 001} high energy crystal face of highlight catalytic active.Can be widely used in fields such as photochemical catalysis, gas sensor and thin-film solar cells.
Description of drawings
Fig. 1 is surface coverage height ratio { the field emission scanning electron microscope photo of the titanium sheet of 001} crystal face monocrystalline anatase titania film of embodiment 1 preparation;
Fig. 2 is the surface coverage height ratio { X-ray diffractogram of the titanium sheet of 001} crystal face monocrystalline anatase titania film of embodiment 1 preparation;
Fig. 3 is surface coverage height ratio { the field emission scanning electron microscope photo in the cross section of the titanium sheet of 001} crystal face monocrystalline anatase titania film of embodiment 1 preparation;
Fig. 4 is surface coverage height ratio { the field emission scanning electron microscope photo of the titanium sheet of 001} crystal face monocrystalline anatase titania film of embodiment 2 preparations;
Fig. 5 is surface coverage height ratio { the field emission scanning electron microscope photo of the titanium sheet of 001} crystal face monocrystalline anatase titania film of embodiment 3 preparations;
Fig. 6 is surface coverage height ratio { the field emission scanning electron microscope photo of the titanium sheet of 001} crystal face monocrystalline anatase titania film of embodiment 4 preparations;
Fig. 7 is surface coverage height ratio { the field emission scanning electron microscope photo of the titanium sheet of 001} crystal face monocrystalline anatase titania film of embodiment 5 preparations;
Fig. 8 is surface coverage height ratio { the field emission scanning electron microscope photo of the titanium sheet of 001} crystal face monocrystalline anatase titania film of embodiment 6 preparations;
Fig. 9 is surface coverage height ratio { the field emission scanning electron microscope photo of the titanium sheet of 001} crystal face monocrystalline anatase titania film of embodiment 7 preparations;
Figure 10 is surface coverage height ratio { the field emission scanning electron microscope photo of the titanium sheet of 001} crystal face monocrystalline anatase titania film of embodiment 8 preparations.
Embodiment
Further set forth the inventive method below in conjunction with embodiment.
1) be that 50～55% hydrofluoric acid, mass concentration are that 65～68% nitric acid mixed with deionized water in 1: 3: 6 by volume with mass concentration, pickle solution;
2) the preparation mass concentration is 0.20% aqueous hydrogen fluoride solution, inserts in the tetrafluoroethylene hydro-thermal jar, and the volume ratio of aqueous hydrogen fluoride solution and hydro-thermal jar is 4: 5;
3) thickness is 2 millimeters the pickle solution pickling of metallic titanium plate with step 1) after; Use the deionized water ultrasonic cleaning clean again, put into tetrafluoroethylene hydro-thermal jar and be immersed in aqueous hydrogen fluoride solution, 180 ℃ of following hydro-thermal reactions 12 hours; Use washed with de-ionized water, drying.
Obtain as shown in Figure 1 by the octahedra monocrystalline of rescinded angle forms attached to the titanium dioxide film on the metallic titanium plate, two parallel surfaces were { the 001} high energy crystal face of monocrystalline about rescinded angle was octahedral.In the X ray diffracting spectrum of Fig. 2, all diffraction peaks are all well corresponding to the anatase octahedrite phase structure among the standard card 21-1272.Cross-section result shown in Figure 3 shows, about 100 microns of titanium oxide film thickness.
Embodiment 2
1) with embodiment 1;
2) the preparation mass concentration is 0.15% aqueous hydrogen fluoride solution, inserts in the tetrafluoroethylene hydro-thermal jar, and the volume ratio of aqueous hydrogen fluoride solution and hydro-thermal jar is 4: 5;
3) with embodiment 1.
Obtain as shown in Figure 4 by the octahedra monocrystalline of rescinded angle form attached to the titanium dioxide film on the metallic titanium plate.
Embodiment 3
1) with embodiment 1;
2) the preparation mass concentration is 0.30% aqueous hydrogen fluoride solution, inserts in the tetrafluoroethylene hydro-thermal jar, and the volume ratio of aqueous hydrogen fluoride solution and hydro-thermal jar is 4: 5;
3) with embodiment 1.
Obtain as shown in Figure 5 basically by the octahedra monocrystalline of rescinded angle form attached to the titanium dioxide film on the metallic titanium plate.
Embodiment 4
1) with embodiment 1;
2) the preparation mass concentration is 0.40% aqueous hydrogen fluoride solution, inserts in the tetrafluoroethylene hydro-thermal jar, and the volume ratio of aqueous hydrogen fluoride solution and hydro-thermal jar is 4: 5;
3) with embodiment 1.
Obtain as shown in Figure 6 basically by the octahedra monocrystalline of rescinded angle form attached to the titanium dioxide film on the metallic titanium plate.
Embodiment 5
1) with embodiment 1;
2) the preparation mass concentration is 0.80% aqueous hydrogen fluoride solution, inserts in the tetrafluoroethylene hydro-thermal jar, and the volume ratio of aqueous hydrogen fluoride solution and hydro-thermal jar is 4: 5;
3) with embodiment 1.
Obtain as shown in Figure 7 basically by the octahedra monocrystalline of rescinded angle form attached to the titanium dioxide film on the metallic titanium plate.
Embodiment 6
1) with embodiment 1;
2) with embodiment 1;
3) thickness is 2 millimeters the pickle solution pickling of metallic titanium plate with step 1) after; Use the deionized water ultrasonic cleaning clean again, put into tetrafluoroethylene hydro-thermal jar and be immersed in aqueous hydrogen fluoride solution, 180 ℃ of following hydro-thermal reactions 3 hours; Use washed with de-ionized water, drying.
Obtain as shown in Figure 8 basically by the octahedra monocrystalline of rescinded angle form attached to the titanium dioxide film on the metallic titanium plate.
Embodiment 7
1) with embodiment 1;
2) with embodiment 1;
3) thickness is 1 millimeter the pickle solution pickling of metallic titanium plate with step 1) after; Use the deionized water ultrasonic cleaning clean again, put into tetrafluoroethylene hydro-thermal jar and be immersed in aqueous hydrogen fluoride solution, 180 ℃ of following hydro-thermal reactions 4 hours; Use washed with de-ionized water, drying.
Obtain as shown in Figure 9 basically by the octahedra monocrystalline of rescinded angle form attached to the titanium dioxide film on the metallic titanium plate.
Embodiment 8
1) with embodiment 1;
2) with embodiment 1;
3) thickness is 2 millimeters the pickle solution pickling of metallic titanium plate with step 1) after; Use the deionized water ultrasonic cleaning clean again, put into tetrafluoroethylene hydro-thermal jar and be immersed in aqueous hydrogen fluoride solution, 180 ℃ of following hydro-thermal reactions 6 hours; Use washed with de-ionized water, drying.
Obtain shown in figure 10 basically by the octahedra monocrystalline of rescinded angle form attached to the titanium dioxide film on the metallic titanium plate.
Claims (1)
1. the preparation method of a monocrystalline anatase titania film may further comprise the steps:
1) be that 50～55% hydrofluoric acid, mass concentration are that 65～68% nitric acid mixed with deionized water in 1: 3: 6 by volume with mass concentration, pickle solution;
2) the preparation mass concentration is 0.15～0.80% aqueous hydrogen fluoride solution, inserts in the tetrafluoroethylene hydro-thermal jar, and the volume ratio of aqueous hydrogen fluoride solution and hydro-thermal jar is 4: 5;
3) thickness is the pickle solution pickling of metallic titanium plate with step 1) more than 1 millimeter after; Use the deionized water ultrasonic cleaning clean again, put into tetrafluoroethylene hydro-thermal jar and be immersed in aqueous hydrogen fluoride solution, 180 ℃ of following hydro-thermal reactions 3～12 hours; Use washed with de-ionized water; Drying obtains attached to the monocrystalline anatase titania film on the metallic titanium plate, and this film is a height ratio { 001} crystal face monocrystalline anatase titania film.
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| CN103936066A (en) * | 2014-05-05 | 2014-07-23 | 浙江大学 | Method for preparing rutile titanium dioxide nanometer flower array thin film |
| CN104032367A (en) * | 2014-05-20 | 2014-09-10 | 中国科学院广州能源研究所 | Method for preparing TiO2 nano nanopillar array by combination of pre-implantation of rutile-phase TiO2 film on titanium substrate and hydrothermal synthesis |
| CN104275170B (en) * | 2014-09-12 | 2016-06-15 | 西安科技大学 | A kind of { 001} face anatase TiO2The normal temperature preparation method of monocrystalline |
| CN105478267B (en) * | 2015-12-24 | 2021-02-19 | 浙江海洋学院 | Spraying system and method for spraying titanium dioxide film on surface of large-area steel body |
| CN106048722B (en) * | 2016-07-13 | 2018-07-24 | 上海工程技术大学 | One kind recycling exposure (001) crystal face TiO from titaniferous waste liquid2Method |
| CN108911056B (en) * | 2018-03-23 | 2021-06-04 | 同济大学 | Preparation and application of {001} crystal face controllable exposure titanium dioxide photoelectrode |
| CN109046302B (en) * | 2018-08-27 | 2021-12-07 | 合肥工业大学 | Porous petal-shaped anatase TiO2Nanocrystalline thin film and preparation method thereof |
| CN111519251B (en) * | 2019-02-01 | 2021-09-21 | 中国科学院福建物质结构研究所 | Titanium dioxide single crystal material and growth method thereof |
| CN111647880B (en) * | 2019-03-04 | 2022-09-02 | 中国科学院宁波材料技术与工程研究所 | Method for growing titanium dioxide nanoparticles on surface of titanium or titanium alloy substrate |
| CN110655106B (en) * | 2019-10-08 | 2022-04-05 | 浙江工业大学 | Method for in-situ preparation of high-energy crystal face exposed titanium dioxide film |
| CN113564707B (en) * | 2021-08-23 | 2022-07-29 | 浙江工业大学 | Method for in-situ preparation of {001} crystal face exposed anatase type titanium dioxide film |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1740392A (en) * | 2005-09-13 | 2006-03-01 | 浙江大学 | Process of preparing directionally arranged nanometer titania rods on the surface of metal titanium |
| CN101396651A (en) * | 2008-10-17 | 2009-04-01 | 浙江大学 | Nano phototranslating composite film in order structure and preparation method thereof |
| CN101508463A (en) * | 2009-03-19 | 2009-08-19 | 浙江大学 | Method for producing nano-wire array film of titanium dioxide |
| CN101767820A (en) * | 2010-01-12 | 2010-07-07 | 浙江大学 | Multi-facet spherical micro-nano-structure titanium dioxide and preparation method thereof |
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| JP2001287996A (en) * | 2000-04-03 | 2001-10-16 | Toho Titanium Co Ltd | Anatase-type titanium oxide single crystal |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1740392A (en) * | 2005-09-13 | 2006-03-01 | 浙江大学 | Process of preparing directionally arranged nanometer titania rods on the surface of metal titanium |
| CN101396651A (en) * | 2008-10-17 | 2009-04-01 | 浙江大学 | Nano phototranslating composite film in order structure and preparation method thereof |
| CN101508463A (en) * | 2009-03-19 | 2009-08-19 | 浙江大学 | Method for producing nano-wire array film of titanium dioxide |
| CN101767820A (en) * | 2010-01-12 | 2010-07-07 | 浙江大学 | Multi-facet spherical micro-nano-structure titanium dioxide and preparation method thereof |
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| JP特开2001-287996A 2001.10.16 |
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