WO2018095290A1 - 一种透明的独立二氧化钛纳米管阵列薄膜的制备方法 - Google Patents

一种透明的独立二氧化钛纳米管阵列薄膜的制备方法 Download PDF

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WO2018095290A1
WO2018095290A1 PCT/CN2017/111793 CN2017111793W WO2018095290A1 WO 2018095290 A1 WO2018095290 A1 WO 2018095290A1 CN 2017111793 W CN2017111793 W CN 2017111793W WO 2018095290 A1 WO2018095290 A1 WO 2018095290A1
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nanotube array
titanium dioxide
array film
dioxide nanotube
temperature
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French (fr)
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沈文浩
童欣
陈小泉
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South China University of Technology SCUT
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    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
    • C25D11/02—Anodisation
    • C25D11/26—Anodisation of refractory metals or alloys based thereon
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G23/00—Compounds of titanium
    • C01G23/04—Oxides; Hydroxides
    • C01G23/047—Titanium dioxide
    • C01G23/0475—Purification
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
    • B01J21/063—Titanium; Oxides or hydroxides thereof
    • 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
    • B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
    • B01J35/39—Photocatalytic properties
    • 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
    • B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
    • B01J35/58—Fabrics or filaments
    • 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
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/08—Heat treatment
    • 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
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/34—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation
    • B01J37/341—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation
    • B01J37/343—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation of ultrasonic wave energy
    • 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
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/34—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation
    • B01J37/348—Electrochemical processes, e.g. electrochemical deposition or anodisation
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G23/00—Compounds of titanium
    • C01G23/04—Oxides; Hydroxides
    • C01G23/047—Titanium dioxide
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • 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
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
    • C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
    • C—CHEMISTRY; METALLURGY
    • 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
    • C01P2004/03—Particle morphology depicted by an image obtained by SEM
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/10—Particle morphology extending in one dimension, e.g. needle-like
    • C01P2004/13—Nanotubes

Definitions

  • the invention relates to the field of preparation of titanium dioxide nanomaterials, in particular to a preparation method of transparent titanium dioxide nanotube array films.
  • Nano titanium dioxide has become one of the hotspots in the research of photocatalytic properties of semiconductor materials due to its excellent photocatalytic performance and no secondary pollution.
  • titanium dioxide nanotubes have a large specific surface area and a special surface morphology, their application to photocatalytic research is bound to bring more possibilities for the improvement of photocatalytic performance.
  • the TiO2 nanotubes are prepared by anodizing method with simple process and mild conditions.
  • the titanium dioxide nanotubes obtained by this method are based on a metal titanium plate and cannot be formed into a film independently, which limits its further development and application. Therefore, under the premise of not destroying the morphology of the titanium dioxide nano-array tube, how to use an effective method to automatically separate it from the substrate and obtain an independent film is an urgent problem to be solved.
  • a titanium dioxide nanotube array of a certain thickness is first obtained by anodization on a titanium substrate, and then subjected to secondary treatment by physical or chemical methods to make the nanotube array film and titanium.
  • Substrate separation The physical methods mainly include: solvent evaporation to separate the film, ultrasonic vibration or directly bonding with a tape to separate the film, but the disadvantage is that it is difficult to obtain a large-area independent titanium dioxide film, which often fails to be separated, and the titanium dioxide tube is destroyed.
  • the morphology; chemical methods mainly include: secondary anodization and chemical solution dissolution.
  • the secondary anodic oxidation method refers to the secondary anodization of the titanium plate by changing the oxidation voltage or the temperature of the electrolyte after the end of the first anodization, in which the film is separated, but the process is relatively complicated.
  • the solution dissolution method is immersed in a chemical reagent to cause the array film to fall off, but it takes a long time.
  • the current process for preparing a titanium dioxide nanotube array film is cumbersome and complicated, and the obtained film has a large thickness and an opaque appearance.
  • the invention adopts a titanium foil as an anode, and prepares a titanium dioxide nanotube array film by anodization method, which does not need to be subjected to secondary treatment, and after high temperature annealing, a complete transparent titanium dioxide nanotube array film is obtained, which saves time and cost. At the same time, it does not destroy the morphology of the film.
  • the object of the present invention is to provide a convenient and effective method for preparing a titanium dioxide nanotube array film which is independent and highly transparent.
  • the present invention adopts the following technical solutions.
  • a method for preparing a transparent independent titanium dioxide nanotube array film comprises the following steps:
  • the pretreated metal titanium foil is used as an anode, the inert electrode is used as a cathode, the cathode and the anode are placed in an organic electrolyte, a voltage is applied, and anodization is performed at room temperature; after the oxidation is completed, the anode is washed with deionized water. , naturally drying, obtaining a metal titanium foil having a titanium dioxide nanotube array film grown on the surface;
  • the metal titanium foil having the titanium dioxide nanotube array film grown on the surface is subjected to high temperature annealing, and after cooling at a high temperature, the film is cooled to room temperature, and the titanium dioxide nanotube array film on the surface of the metal titanium foil is peeled off to obtain the transparent independent titanium dioxide nanotube array. film.
  • the metal titanium foil has a thickness of 0.01 to 0.02 mm, and the metal titanium foil has a purity of 99.0 to 99.9%.
  • the pretreatment is to ultrasonically clean the metal titanium foil in acetone, ethanol and deionized water for 10-20 min to remove the oil stain on the surface of the metal titanium foil, and then dry naturally.
  • the inert electrode comprises a platinum electrode, a graphite electrode or a gold electrode.
  • the organic electrolytic solution is an ethylene glycol solution containing 0.55 wt% of ammonium fluoride and 5 to 20 wt% of deionized water.
  • the voltage applied during the anodization is 30V.
  • the anodization time is 2-6 h.
  • the high-temperature annealing is performed by raising the temperature to 450 ° C at a heating rate of 10 ° C / min in an air atmosphere for 2 to 6 hours.
  • the temperature rising program of the high temperature annealing is: raising the temperature to 100 ° C at a heating rate of 10 ° C / min, keeping the temperature 10 Min, then increase the temperature to 200 ° C at a heating rate of 10 ° C / min, keep warm 10 Min; at the temperature increase rate of 10 ° C / min, the temperature was also increased to 300 ° C and 400 ° C, respectively, for 10 min, until the temperature was raised to 450 ° C.
  • the titanium dioxide in the titanium dioxide nanotube array film prepared by the above preparation method is an anatase crystal form.
  • the present invention has the following advantages and benefits:
  • the present invention does not require additional physical or chemical treatment for secondary treatment, and the titanium dioxide nanotube array film obtained by anodizing on the surface of the metal titanium foil is subjected to high temperature annealing after the metal titanium foil is used as a substrate, and the titanium dioxide nanotube array film is naturally Shedding gives a transparent, independent, complete titanium dioxide nanotube array film.
  • the method of the invention is simple in operation, saves time and cost, and prepares a completely peelable titanium dioxide nanotube array film without destroying the morphology of the titanium dioxide tube; the independent and complete titanium dioxide nanotube array film is convenient for transfer and post-processing, and It has transparent properties and can be better applied to research such as photocatalysis.
  • 1a and 1b are SEM images of different folds of the front side of the transparent independent titanium dioxide nanotube array film prepared in Example 2;
  • Example 2a is an SEM image of the side of the transparent independent titanium dioxide nanotube array film prepared in Example 2;
  • Example 2b is an SEM image of the bottom surface of the transparent independent titanium dioxide nanotube array film prepared in Example 2;
  • Example 3 is an EDS analysis diagram of a transparent independent titanium dioxide nanotube array film prepared in Example 2;
  • Example 4 is an XRD pattern of the titanium dioxide nanotube array film prepared in Example 2 after heat treatment at 450 ° C.
  • metal titanium foil purity of 99.9%, thickness of 0.01
  • the metal titanium foil of mm was cut into rectangles, and ultrasonically cleaned in acetone, ethanol and deionized water for 10 min in order to remove the oil stain on the surface of the metal titanium foil, and finally dried naturally for use.
  • the pretreated metal titanium foil is connected to the positive electrode of the power supply, and the graphite electrode is connected to the negative electrode.
  • the distance between the two poles is 2.5.
  • the electrolyte is an ethylene glycol solution containing 0.55 wt% ammonium fluoride and 20 wt% deionized water, anodizing at 30 V at room temperature 2 h; After the reaction is completed, the prepared sample is washed with deionized water and naturally dried to obtain a metal titanium foil having a titanium oxide nanotube array film grown on its surface.
  • the average diameter of the titanium dioxide nanotubes in the obtained transparent independent titanium dioxide nanotube array film is 110 nm, and the average wall thickness of the tube is 13 Nm, tube length 3.8 ⁇ m; through the titanium dioxide nanotube array film, the text on the paper placed under the film can be clearly seen.
  • metal titanium foil purity of 99.7 %, thickness of 0.01
  • the metal titanium foil of mm was cut into rectangles, and ultrasonically cleaned in acetone, ethanol and deionized water for 10 min in order to remove the oil stain on the surface of the metal titanium foil, and finally dried naturally for use.
  • the pretreated metal titanium foil is connected to the positive electrode of the power supply, and the platinum electrode is connected to the negative electrode.
  • the distance between the two poles is 2.5.
  • the electrolyte is an ethylene glycol solution containing 0.55 wt% ammonium fluoride and 20 wt% deionized water, anodizing at 30 V at room temperature 2 h; After the reaction is completed, the prepared sample is washed with deionized water and naturally dried to obtain a metal titanium foil having a titanium oxide nanotube array film grown on its surface.
  • the SEM images of the different fronts of the obtained transparent independent titanium dioxide nanotube array film are shown in Fig. 1a and Fig. 1b.
  • the average diameter of the titanium dioxide nanotubes in the film is 110.
  • Nm the average wall thickness of the tube is 13 nm.
  • the SEM images of the side and bottom surfaces of the obtained transparent independent titanium dioxide nanotube array film are shown in Fig. 2a and Fig. 2b, respectively. It can be seen from Fig. 2a and Fig. 2b that the obtained film has a complete morphology and the tube of the titanium dioxide nanotube in the film. Length 3.8 Mm.
  • FIG. 3 is an EDS analysis diagram of the obtained transparent independent titanium dioxide nanotube array film. It can be seen from FIG. 3 that the film contains only titanium and oxygen, and the titanium dioxide nanotubes are further determined.
  • FIG. 4 is an XRD pattern of the prepared titanium dioxide nanotubes after heat treatment at 450 ° C. It can be seen from the figure that the curves except the diffraction peaks of the titanium metal matrix (40°, 53°, 70°, and 76°) are simultaneously at 25°. The diffraction peaks of anatase phase appear near 38°, 48° and 55°, which are consistent with the anatase phase titanium dioxide standard card, indicating that the nanotube array film is anatase phase titanium dioxide.
  • the text on the paper placed under the film can be clearly seen, indicating that the method is an independently transparent titanium dioxide nanotube array film.
  • metal titanium foil purity of 99.0%, thickness of 0.01
  • the metal titanium foil of mm was cut into rectangles, and ultrasonically cleaned in acetone, ethanol and deionized water for 20 min in order to remove the oil stain on the surface of the metal titanium foil, and finally dried naturally for use.
  • the pretreated metal titanium foil is connected to the positive electrode of the power supply, and the platinum electrode is connected to the negative electrode.
  • the distance between the two poles is 2.5.
  • the electrolyte is an ethylene glycol solution containing 0.55 wt% ammonium fluoride and 20 wt% deionized water, anodizing at 30 V at room temperature 2 h; After the reaction is completed, the prepared sample is washed with deionized water and naturally dried to obtain a metal titanium foil having a titanium oxide nanotube array film grown on its surface.
  • the average diameter of the titanium dioxide nanotubes in the film is 110 nm, the average wall thickness of the tube is 13 nm, and the tube length is 3.8. Mm; through the titanium dioxide nanotube array film, the text on the paper placed under the film can be clearly seen.
  • metal titanium foil purity of 99.7 % and thickness of 0.02
  • the metal titanium foil of mm was cut into a rectangular shape, and ultrasonically cleaned in acetone, ethanol and deionized water for 15 min in order to remove the oil stain on the surface of the metal titanium foil, and finally dried naturally for use.
  • the pretreated metal titanium foil is connected to the positive electrode of the power supply, and the platinum electrode is connected to the negative electrode.
  • the distance between the two poles is 2.5.
  • the electrolyte is an ethylene glycol solution containing 0.55 wt% ammonium fluoride and 20 wt% deionized water, anodizing at 30 V at room temperature 2 h; After the reaction is completed, the prepared sample is washed with deionized water and naturally dried to obtain a metal titanium foil having a titanium oxide nanotube array film grown on its surface.
  • the average diameter of the titanium dioxide nanotubes in the film is 110 nm, the average wall thickness of the tube is 13 nm, and the tube length is 3.8. Mm; through the titanium dioxide nanotube array film, the text on the paper placed under the film can be clearly seen.
  • metal titanium foil purity of 99.7 %, thickness of 0.01
  • the metal titanium foil of mm was cut into rectangles, and ultrasonically cleaned in acetone, ethanol and deionized water for 10 min in order to remove the oil stain on the surface of the metal titanium foil, and finally dried naturally for use.
  • the pretreated metal titanium foil is connected to the positive electrode of the power supply, and the platinum electrode is connected to the negative electrode.
  • the distance between the two poles is 2.5.
  • the electrolyte is an ethylene glycol solution containing 0.55 wt% ammonium fluoride and 20 wt% deionized water at room temperature, 30
  • the V voltage was anodized for 6 hours; after the reaction was completed, the prepared sample was washed with deionized water and naturally dried to obtain a metal titanium foil having a titanium oxide nanotube array film grown on the surface.
  • the average diameter of the titanium dioxide nanotubes in the obtained transparent independent titanium dioxide nanotube array film is 110 nm, and the average wall thickness of the tube is 13 Nm, tube length 7.1 ⁇ m; through the titanium dioxide nanotube array film, the text on the paper placed under the film can be clearly seen.
  • metal titanium foil purity of 99.7 %, thickness of 0.01
  • the metal titanium foil of mm was cut into rectangles, and ultrasonically cleaned in acetone, ethanol and deionized water for 10 min in order to remove the oil stain on the surface of the metal titanium foil, and finally dried naturally for use.
  • the pretreated metal titanium foil is connected to the positive electrode of the power supply, and the platinum electrode is connected to the negative electrode.
  • the distance between the two poles is 2.5.
  • the electrolyte is an ethylene glycol solution containing 0.55 wt% ammonium fluoride and 15 wt% deionized water at room temperature, 30
  • the V voltage was anodized for 4 hours; after the reaction was completed, the prepared sample was washed with deionized water and naturally dried to obtain a metal titanium foil having a titanium oxide nanotube array film grown on the surface.
  • the average diameter of the titanium dioxide nanotubes in the obtained transparent independent titanium dioxide nanotube array film is 90 nm, and the average wall thickness of the tube is 22 Nm, tube length 6.7 ⁇ m; through the titanium dioxide nanotube array film, the text on the paper placed under the film can be clearly seen.
  • metal titanium foil purity of 99.7 %, thickness of 0.01
  • the metal titanium foil of mm was cut into rectangles, and ultrasonically cleaned in acetone, ethanol and deionized water for 10 min in order to remove the oil stain on the surface of the metal titanium foil, and finally dried naturally for use.
  • the pretreated metal titanium foil is connected to the positive electrode of the power supply, and the platinum electrode is connected to the negative electrode.
  • the distance between the two poles is 2.5.
  • the electrolyte is an ethylene glycol solution containing 0.55 wt% ammonium fluoride and 5 wt% deionized water, at room temperature, at 30
  • the V voltage was anodized for 4 hours; after the reaction was completed, the prepared sample was washed with deionized water and naturally dried to obtain a metal titanium foil having a titanium oxide nanotube array film grown on the surface.
  • the average diameter of the titanium dioxide nanotubes in the transparent independent titanium dioxide nanotube array film is 50 nm, the average wall thickness of the tube is 30 nm, and the tube length is 6.7 ⁇ m; the titanium dioxide nanotube array film can be clearly seen through the film.

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Abstract

本发明公开了一种透明的独立二氧化钛纳米管阵列薄膜的制备方法。该方法以金属钛箔为基底，在金属钛箔表面经阳极氧化得到的二氧化钛纳米管阵列薄膜通过高温退火后，二氧化钛纳米管阵列膜自然脱落，得到透明的独立二氧化钛纳米管阵列薄膜。本发明方法操作简单，节约时间及成本，制备出可完整剥离的二氧化钛纳米管阵列薄膜，且不破坏二氧化钛管的形貌；独立完整的二氧化钛纳米管阵列薄膜方便转移及后加工，且具有透明特性，能更好地应用于光催化等研究中。

Description

一种透明的独立二氧化钛纳米管阵列薄膜的制备方法
技术领域
本发明涉及二氧化钛纳米材料制备领域，具体涉及一种透明的二氧化钛纳米管阵列薄膜的制备方法。
背景技术
随着人们对环境污染问题的关注度日益提升，将纳米技术和半导体光催化技术相结合，将其应用于环境保护方面，给环境污染的治理带来了新的机遇。纳米二氧化钛以其优异的光催化性能、不产生二次污染等优点，成为半导体材料光催化性能研究的热点之一。另外，由于二氧化钛纳米管具有比表面积大，表面形貌特殊，将其应用于光催化研究，势必将为光催化性能的提升，带来更多的可能性。采用阳极氧化法制备二氧化钛纳米管，工艺简单，条件温和，但是通过该方法获得的二氧化钛纳米管是以金属钛板作为基底，无法独立成膜，限制了对其进一步的开发及应用。因此，在不破坏二氧化钛纳米阵列管形貌的前提下，如何采用有效的方法使其自动脱离基底，获得独立的薄膜是亟待解决的问题。
目前，为获得独立的二氧化钛纳米管阵列薄膜，一般首先通过阳极氧化法在钛基底上获得一定厚度的二氧化钛纳米管阵列，再通过物理或化学方法对其进行二次处理使纳米管阵列膜与钛基底分离。物理方法主要包括：溶剂蒸发使薄膜分离、超声振荡或直接用胶带粘下使薄膜分离，但其缺点是很难获得大面积完整的独立二氧化钛薄膜，经常出现无法分离的情况，且会破坏二氧化钛管的形貌；化学方法主要包括：二次阳极氧化和化学溶液溶解的方法。二次阳极氧化法是指在第一次阳极氧化结束后，通过改变氧化电压或电解液温度对钛板进行二次阳极氧化，在该过程中使薄膜分离，但是工艺相对较复杂。溶液溶解法是采用化学试剂浸泡，使阵列膜脱落，但耗时较长。总之，目前制备二氧化钛纳米管阵列薄膜的过程繁琐复杂，且获得的膜厚度较大，外观不透明。本发明以钛箔为阳极，通过阳极氧化法制备二氧化钛纳米管阵列膜，无需对其进行二次处理，经过高温退火后，即获得完整透明的二氧化钛纳米管阵列膜，该方法节约时间及成本，同时不破坏膜的形貌。
发明内容
本发明的目的在于提供一种便捷有效的，可获得独立且透明度高的二氧化钛纳米管阵列薄膜的制备方法。
为实现上述目的，本发明采用如下的技术方案。
一种透明的独立二氧化钛纳米管阵列薄膜的制备方法，包括如下步骤：
（1）以经过预处理的金属钛箔作为阳极，惰性电极作为阴极，将阴极和阳极置于有机电解液中，施加电压，室温下进行阳极氧化；氧化结束后，将阳极用去离子水清洗，自然干燥，得到表面生长有二氧化钛纳米管阵列薄膜的金属钛箔；
（2）将表面生长有二氧化钛纳米管阵列薄膜的金属钛箔进行高温退火，高温退火结束后冷却至室温，金属钛箔表面的二氧化钛纳米管阵列薄膜脱落，得到所述透明的独立二氧化钛纳米管阵列薄膜。
进一步地，步骤（1）中，所述金属钛箔的厚度为0.01-0.02mm，金属钛箔的纯度为99.0-99.9%。
进一步地，步骤（1）中，所述预处理是将金属钛箔依次在丙酮、乙醇和去离子水中进行超声清洗10-20min，以去除金属钛箔表面的油污，再自然晾干。
进一步地，步骤（1）中，所述惰性电极包括铂电极、石墨电极或金电极。
进一步地，步骤（1）中，所述有机电解液为含有0.55wt%氟化铵和5-20wt%去离子水的乙二醇溶液。
进一步地，步骤（1）中，阳极氧化过程中施加的电压为30V。
进一步地，步骤（1）中，所述阳极氧化的时间为2-6h。
进一步地，步骤（2）中，所述高温退火是在空气气氛中，以10℃/min的升温速率升温至450℃并保温2-6小时。
更进一步地，步骤（2）中，所述高温退火的升温程序为：以10℃/min的升温速率升温至100℃，保温10 min，再以10℃/min的升温速率升温至200℃，保温10 min；以10℃/min的升温速率在升温至300℃和400℃时同样分别保温10min，直至升温至450℃。
上述制备方法制得的二氧化钛纳米管阵列薄膜中的二氧化钛为锐钛矿晶型。
与现有技术相比，本发明具有如下优点和有益效果：
（1）本发明无需另外采用物理或化学方法进行二次处理，以金属钛箔为基底，在金属钛箔表面经阳极氧化得到的二氧化钛纳米管阵列薄膜通过高温退火后，二氧化钛纳米管阵列膜自然脱落，得到透明的独立完整的二氧化钛纳米管阵列薄膜。
（2）本发明方法操作简单，节约时间及成本，制备出可完整剥离的二氧化钛纳米管阵列薄膜，且不破坏二氧化钛管的形貌；独立完整的二氧化钛纳米管阵列薄膜方便转移及后加工，且具有透明特性，能更好地应用于光催化等研究中。
附图说明
图1a和图1b为实施例2制得的透明的独立二氧化钛纳米管阵列薄膜正面不同倍数的SEM图；
图2a为实施例2制得的透明的独立二氧化钛纳米管阵列薄膜侧面的SEM图；
图2b为实施例2制得的透明的独立二氧化钛纳米管阵列薄膜底面的SEM图；
图3为实施例2制得的透明的独立二氧化钛纳米管阵列薄膜的EDS分析图；
图4为实施例2制备得到的二氧化钛纳米管阵列薄膜在450℃下热处理后的XRD图。
具体实施方式
下面结合实施例对本发明作进一步描述，这些实施例只是用于说明本发明，并不限制本发明。
实施例1
（1）金属钛箔的预处理：将纯度为99.9 %、厚度为0.01 mm的金属钛箔剪切为矩形，依次在丙酮、乙醇、去离子水中进行超声清洗10 min，以去除金属钛箔表面的油污，最后自然晾干备用。
（2）阳极氧化：以预处理好的金属钛箔接电源正极，以石墨电极接负极，两极间距离2.5 cm，电解液为含有0.55 wt% 氟化铵和20 wt%去离子水的乙二醇溶液，在室温下，以30 V电压阳极氧化2 h；反应结束后，将制得的样品用去离子水清洗，自然干燥，得到表面生长有二氧化钛纳米管阵列薄膜的金属钛箔。
（3）高温退火：将表面生长有二氧化钛纳米管阵列薄膜的金属钛箔置于马弗炉中，以10℃/min的升温速率升温至100℃，保温10 min，再以10℃/min的升温速率升温至200℃，保温10 min；以10℃/min的升温速率在升温至300℃和400℃时同样分别保温10min，直至升温至450℃，保温2 h后，随炉冷却至室温，得到具有锐钛矿晶型的透明的独立二氧化钛纳米管阵列薄膜。
得到的透明的独立二氧化钛纳米管阵列薄膜中的二氧化钛纳米管的平均管径为110 nm，管的平均壁厚13 nm，管长3.8 μm；透过二氧化钛纳米管阵列薄膜，能够清晰地看到放在膜下方的纸上的文字。
实施例2
（1）金属钛箔的预处理：将纯度为99.7 %、厚度为0.01 mm的金属钛箔剪切为矩形，依次在丙酮、乙醇、去离子水中进行超声清洗10 min，以去除金属钛箔表面的油污，最后自然晾干备用。
（2）阳极氧化：以预处理好的金属钛箔接电源正极，以铂电极接负极，两极间距离2.5 cm，电解液为含有0.55 wt% 氟化铵和20 wt%去离子水的乙二醇溶液，在室温下，以30 V电压阳极氧化2 h；反应结束后，将制得的样品用去离子水清洗，自然干燥，得到表面生长有二氧化钛纳米管阵列薄膜的金属钛箔。
（3）高温退火：将表面生长有二氧化钛纳米管阵列薄膜的金属钛箔置于马弗炉中，以10℃/min的升温速率升温至100℃，保温10 min，再以10℃/min的升温速率升温至200℃，保温10 min；以10℃/min的升温速率在升温至300℃和400℃时同样分别保温10min，直至升温至450℃，保温2 h后，随炉冷却至室温，得到具有锐钛矿晶型的透明的独立二氧化钛纳米管阵列薄膜。
得到的透明的独立二氧化钛纳米管阵列薄膜的正面不同倍数的SEM图如图1a和图1b所示，由图1a和图1b可知，薄膜中的二氧化钛纳米管的平均管径为110 nm，管的平均壁厚13 nm。
得到的透明的独立二氧化钛纳米管阵列薄膜的侧面和底面的SEM图分别如图2a和图2b所示，由图2a和图2b可知，得到的薄膜形貌完整，薄膜中的二氧化钛纳米管的管长3.8 μm。
图3为制得的透明的独立二氧化钛纳米管阵列薄膜的EDS分析图，由图3可知该膜仅含有钛与氧两种元素，进一步确定成功制得二氧化钛纳米管。
图4为制备得到的二氧化钛纳米管在450℃下热处理后的XRD图，由图可知，曲线除了金属钛基体的衍射峰（40°、53°、70°及76°），同时在25°、38°、48°、55°附近出现的均是锐钛矿相的衍射峰，与锐钛矿相二氧化钛标准卡相符合，说明纳米管阵列薄膜为锐钛矿相二氧化钛。
另外透过二氧化钛纳米管阵列薄膜，能够清晰地看到放在膜下方的纸上的文字，说明本方法得到的为独立透明的二氧化钛纳米管阵列薄膜。
实施例3
（1）金属钛箔的预处理：将纯度为99.0 %、厚度为0.01 mm的金属钛箔剪切为矩形，依次在丙酮、乙醇、去离子水中进行超声清洗20 min，以去除金属钛箔表面的油污，最后自然晾干备用。
（2）阳极氧化：以预处理好的金属钛箔接电源正极，以铂电极接负极，两极间距离2.5 cm，电解液为含有0.55 wt% 氟化铵和20 wt%去离子水的乙二醇溶液，在室温下，以30 V电压阳极氧化2 h；反应结束后，将制得的样品用去离子水清洗，自然干燥，得到表面生长有二氧化钛纳米管阵列薄膜的金属钛箔。
（3）高温退火：将表面生长有二氧化钛纳米管阵列薄膜的金属钛箔置于马弗炉中，以10℃/min的升温速率升温至100℃，保温10 min，再以10℃/min的升温速率升温至200℃，保温10 min；以10℃/min的升温速率在升温至300℃和400℃时同样分别保温10min，直至升温至450℃，保温4 h后，随炉冷却至室温，得到具有锐钛矿晶型的透明的独立二氧化钛纳米管阵列薄膜。
薄膜中的二氧化钛纳米管的平均管径为110 nm，管的平均壁厚13 nm，管长3.8 μm；透过二氧化钛纳米管阵列薄膜，能够清晰地看到放在膜下方的纸上的文字。
实施例4
（1）金属钛箔的预处理：将纯度为99.7 %、厚度为0.02 mm的金属钛箔剪切为矩形，依次在丙酮、乙醇、去离子水中进行超声清洗15 min，以去除金属钛箔表面的油污，最后自然晾干备用。
（2）阳极氧化：以预处理好的金属钛箔接电源正极，以铂电极接负极，两极间距离2.5 cm，电解液为含有0.55 wt% 氟化铵和20 wt%去离子水的乙二醇溶液，在室温下，以30 V电压阳极氧化2 h；反应结束后，将制得的样品用去离子水清洗，自然干燥，得到表面生长有二氧化钛纳米管阵列薄膜的金属钛箔。
（3）高温退火：将表面生长有二氧化钛纳米管阵列薄膜的金属钛箔置于马弗炉中，以10℃/min的升温速率升温至100℃，保温10 min，再以10℃/min的升温速率升温至200℃，保温10 min；以10℃/min的升温速率在升温至300℃和400℃时同样分别保温10min，直至升温至450℃，保温6 h后，随炉冷却至室温，得到具有锐钛矿晶型的透明的独立二氧化钛纳米管阵列薄膜。
薄膜中的二氧化钛纳米管的平均管径为110 nm，管的平均壁厚13 nm，管长3.8 μm；透过二氧化钛纳米管阵列薄膜，能够清晰地看到放在膜下方的纸上的文字。
实施例5
（1）金属钛箔的预处理：将纯度为99.7 %、厚度为0.01 mm的金属钛箔剪切为矩形，依次在丙酮、乙醇、去离子水中进行超声清洗10 min，以去除金属钛箔表面的油污，最后自然晾干备用。
（2）阳极氧化：以预处理好的金属钛箔接电源正极，以铂电极接负极，两极间距离2.5 cm，电解液为含有0.55 wt% 氟化铵和20 wt%去离子水的乙二醇溶液，在室温下，以30 V电压阳极氧化6h；反应结束后，将制得的样品用去离子水清洗，自然干燥，得到表面生长有二氧化钛纳米管阵列薄膜的金属钛箔。
（3）高温退火：将表面生长有二氧化钛纳米管阵列薄膜的金属钛箔置于马弗炉中，以10℃/min的升温速率升温至100℃，保温10 min，再以10℃/min的升温速率升温至200℃，保温10 min；以10℃/min的升温速率在升温至300℃和400℃时同样分别保温10min，直至升温至450℃，保温2 h后，随炉冷却至室温，得到具有锐钛矿晶型的透明的独立二氧化钛纳米管阵列薄膜。
得到的透明的独立二氧化钛纳米管阵列薄膜中的二氧化钛纳米管的平均管径为110 nm，管的平均壁厚13 nm，管长7.1 μm；透过二氧化钛纳米管阵列薄膜，能够清晰地看到放在膜下方的纸上的文字。
实施例6
（1）金属钛箔的预处理：将纯度为99.7 %、厚度为0.01 mm的金属钛箔剪切为矩形，依次在丙酮、乙醇、去离子水中进行超声清洗10 min，以去除金属钛箔表面的油污，最后自然晾干备用。
（2）阳极氧化：以预处理好的金属钛箔接电源正极，以铂电极接负极，两极间距离2.5 cm，电解液为含有0.55 wt% 氟化铵和15 wt%去离子水的乙二醇溶液，在室温下，以30 V电压阳极氧化4h；反应结束后，将制得的样品用去离子水清洗，自然干燥，得到表面生长有二氧化钛纳米管阵列薄膜的金属钛箔。
（3）高温退火：将表面生长有二氧化钛纳米管阵列薄膜的金属钛箔置于马弗炉中，以10℃/min的升温速率升温至100℃，保温10 min，再以10℃/min的升温速率升温至200℃，保温10 min；以10℃/min的升温速率在升温至300℃和400℃时同样分别保温10min，直至升温至450℃，保温2 h后，随炉冷却至室温，得到具有锐钛矿晶型的透明的独立二氧化钛纳米管阵列薄膜。
得到的透明的独立二氧化钛纳米管阵列薄膜中的二氧化钛纳米管的平均管径为90 nm，管的平均壁厚22 nm，管长6.7 μm；透过二氧化钛纳米管阵列薄膜，能够清晰地看到放在膜下方的纸上的文字。
实施例7
（1）金属钛箔的预处理：将纯度为99.7 %、厚度为0.01 mm的金属钛箔剪切为矩形，依次在丙酮、乙醇、去离子水中进行超声清洗10 min，以去除金属钛箔表面的油污，最后自然晾干备用。
（2）阳极氧化：以预处理好的金属钛箔接电源正极，以铂电极接负极，两极间距离2.5 cm，电解液为含有0.55 wt% 氟化铵和5 wt%去离子水的乙二醇溶液，在室温下，以30 V电压阳极氧化4h；反应结束后，将制得的样品用去离子水清洗，自然干燥，得到表面生长有二氧化钛纳米管阵列薄膜的金属钛箔。
（3）高温退火：将表面生长有二氧化钛纳米管阵列薄膜的金属钛箔置于马弗炉中，以10℃/min的升温速率升温至100℃，保温10 min，再以10℃/min的升温速率升温至200℃，保温10 min；以10℃/min的升温速率在升温至300℃和400℃时同样分别保温10min，直至升温至450℃，保温2 h后，随炉冷却至室温，得到具有锐钛矿晶型的透明的独立二氧化钛纳米管阵列薄膜。
得到的透明的独立二氧化钛纳米管阵列薄膜中的二氧化钛纳米管的平均管径为50 nm，管的平均壁厚30 nm，管长6.7 μm；透过二氧化钛纳米管阵列薄膜，能够清晰地看到放在膜下方的纸上的文字。

Claims (9)

  1. 一种透明的独立二氧化钛纳米管阵列薄膜的制备方法，其特征在于，包括如下步骤：
    （1）以经过预处理的金属钛箔作为阳极，惰性电极作为阴极，将阴极和阳极置于有机电解液中，施加电压，室温下进行阳极氧化；氧化结束后，将阳极用去离子水清洗，自然干燥，得到表面生长有二氧化钛纳米管阵列薄膜的金属钛箔；
    （2）将表面生长有二氧化钛纳米管阵列薄膜的金属钛箔进行高温退火，高温退火结束后冷却至室温，金属钛箔表面的二氧化钛纳米管阵列薄膜脱落，得到所述透明的独立二氧化钛纳米管阵列薄膜。
  2. 根据权利要求1所述的一种透明的独立二氧化钛纳米管阵列薄膜的制备方法，其特征在于，步骤（1）中，所述金属钛箔的厚度为0.01-0.02mm，金属钛箔的纯度为99.0-99.9%。
  3. 根据权利要求1所述的一种透明的独立二氧化钛纳米管阵列薄膜的制备方法，其特征在于，步骤（1）中，所述预处理是将金属钛箔依次在丙酮、乙醇和去离子水中进行超声清洗10-20min后，自然晾干。
  4. 根据权利要求1所述的一种透明的独立二氧化钛纳米管阵列薄膜的制备方法，其特征在于，步骤（1）中，所述惰性电极包括铂电极、石墨电极或金电极。
  5. 根据权利要求1所述的一种透明的独立二氧化钛纳米管阵列薄膜的制备方法，其特征在于，步骤（1）中，所述有机电解液为含有0.55wt%氟化铵和5-20wt%去离子水的乙二醇溶液。
  6. 根据权利要求1所述的一种透明的独立二氧化钛纳米管阵列薄膜的制备方法，其特征在于，步骤（1）中，阳极氧化过程中施加的电压为30V。
  7. 根据权利要求1所述的一种透明的独立二氧化钛纳米管阵列薄膜的制备方法，其特征在于，步骤（1）中，所述阳极氧化的时间为2-6h。
  8. 根据权利要求1所述的一种透明的独立二氧化钛纳米管阵列薄膜的制备方法，其特征在于，步骤（2）中，所述高温退火是在空气气氛中，以10℃/min的升温速率升温至450℃并保温2-6小时。
  9. 根据权利要求8所述的一种透明的独立二氧化钛纳米管阵列薄膜的制备方法，其特征在于，步骤（2）中，所述高温退火的升温程序为：以10℃/min的升温速率升温至100℃，保温10 min，再以10℃/min的升温速率升温至200℃，保温10 min；以10℃/min的升温速率在升温至300℃和400℃时同样分别保温10min，直至升温至450℃。
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