CN105369323A - Preparing method for forked titanium dioxide nanotube array - Google Patents
Preparing method for forked titanium dioxide nanotube array Download PDFInfo
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- CN105369323A CN105369323A CN201510726449.0A CN201510726449A CN105369323A CN 105369323 A CN105369323 A CN 105369323A CN 201510726449 A CN201510726449 A CN 201510726449A CN 105369323 A CN105369323 A CN 105369323A
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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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
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Abstract
The invention discloses a preparing method for a forked titanium dioxide nanotube array. The preparing method includes the following steps that a pretreatment process is conducted; an anodic oxidation process is conducted; and an annealing process is conducted. Compared with the prior art, due to the fact that prepared titanium dioxide is hollow, a hole is filled with various semiconductor or conductor materials, PN nodes of a semiconductor are prepared, and a diode or triode array is formed. The semiconductor has more superior performance than that of a semiconductor prepared through N type doping and P type doping in a close contact manner, a capacitive material can also be used for filling, and a supercapacitor is prepared.
Description
Technical field
The invention belongs to the preparation method of nano material, belong to the preparation method of branch type titania nanotube especially.
Background technology
Nano tube array of titanium dioxide is widely used in fields such as photoelectricity, electromagnetism and catalysis.CN201310177510 provides a kind of three-dimensional order metal nano-tube array electrode and preparation method thereof: porous-film is fixed on electrode surface, by being electrochemically-deposited in electrode surface directly to growing nano stub array in the duct of porous-film, electroless plating or electrochemical deposition alloy nanotube is continued in the duct of porous-film, alloy nanometer pipe array electrode removal alloying, obtain the nano tube made from noble metal array electrode with tube wall belt hole, in membrane removal liquid, remove porous-film template, obtain the three-dimensional order nano tube made from noble metal array electrode integrating one with electrode.CN201310370880 provides a kind of preparation method of titania nanotube.Its preparation method is: titanium sheet is put into the mixing solutions of ethanol and the acetone prepared or the mixing solutions of Virahol and acetone, be then placed in ultrasonic apparatus ultrasonication; Titanium sheet, graphite are placed in electrolyzing hydrofluoric acid liquor, and under normal temperature state, take titanium sheet as anode, graphite is negative electrode, carries out anodic oxidation, the titanium sheet after oxidation rinsed, ultrasonication, and roasting, cooling obtains titania nanotube.CN200610035732 provides a kind of preparation method of high length-diameter ratio titania nanometer tube array.Its preparation method is: polished by substrate material surface, clean up; Preparation electrolytic solution, and add alcohols additive; Carry out electrochemical anodic oxidation with metal sheet as to electrode, the TiO2 film of Nano tube array with high length-diameter ratio can be obtained at substrate material surface.CN201410143733 provides a kind of pulse anodic oxidation and prepares method prepared by high-sequential titanium dioxide nano-pipe array thin film.Its preparation method is: with the titanium dioxide nano-pipe array thin film of square wave anodizing technology at metallic titanium matrix surface in situ synthesis high-sequential.The titanium dioxide nano-pipe array thin film obtained is the titanium dioxide nano-pipe array thin film with high-sequential.There is the defect of high cost in above-mentioned preparation method, maybe can only obtain the nano-tube array in single aperture, is difficult to the pattern obtaining expecting.
Summary of the invention
Technical problem to be solved by this invention is to provide a kind of preparation method of Nano tube array of titanium dioxide of morphology controllable.
The technical scheme of technical solution problem of the present invention is: a kind of preparation method of branch type Nano tube array of titanium dioxide, comprises the following steps: pretreatment process, anodic oxidation operation, annealing operation.
Described pretreatment process comprises successively:
1) high temperature annealing operation: after titanium sheet being cleaned in ethanol, dries, then puts into retort furnace, and with 5-15 degree/min of temperature programming to 450-530 degree, insulation 4-6h, is chilled to room temperature naturally with stove;
2) ultrasonic cleaning operation: the titanium sheet that high temperature annealing is good to be placed in ethanolic soln (ethanol: the volume ratio of deionized water is 1:1-2) ultrasonic vibration 10-20min in ultrasonic bath, then clean, air-dry stand-by by washed with de-ionized water;
3) chemical rightenning operation: when room temperature, by the titanium sheet of above-mentioned ultrasonic cleaning, is placed in the hydrofluoric acid solution of 0.01-0.05mol/L, soaks 5-20 minute, uses deionized water rinsing immediately, be transferred to oxidation trough after polishing is complete;
Described anodic oxidation operation comprises the following steps:
4) an anodic oxidation operation: under room temperature, make negative electrode with graphite flake, the titanium sheet that electrochemical etching is good is anode, and at the glycerine solution Anodic Oxidation 1-3h containing 0.1-0.3wt% Sodium Fluoride (Neutral ammonium fluoride), voltage is 30-60V;
5) except anodic oxidation membrane process: by titanium sheet good for an anodic oxidation in containing the phosphoric acid of mass concentration 6-10% and the chromic acid mixing solutions water-bath 3-10h of mass concentration 1-5% respectively, temperature is 40-80 degree;
6) two-step anodization operation: at the glycerine solution Anodic Oxidation 1-3h containing 0.1-0.3wt% Sodium Fluoride (Neutral ammonium fluoride) under room temperature, voltage is 30-60V; Regulating voltage is original
continue anodic oxidation 1-3 hour, be placed in deionized water and soak, rinse dry;
Described annealing operation is:
7) annealing operation: the titanium sheet handled well by two-step anodization puts into retort furnace, 300-500 degree carries out anneal, heat-up rate 5-20 degree/min, and constant temperature 1-4h, is cooled to room temperature.
Tube diameters and the anodised voltage of anodic oxidation synthesis of nano pipe array have certain relation.In secondary oxidation operation, the voltage of second step is the first step voltage
time (21.2-42.4V), the tube diameters that second step obtains just only has 1/2 of back, and an original nanotube is just divided into two, forms branch type nano-tube array.The present invention is by regulating the first step anodic oxidation voltage to be 30-60V, and second step anodic oxidation voltage is previous
(i.e. 21.2-42.4V).
In the present invention, high temperature annealing operation is fully eliminated broken to the stress produced in titanium sheet when colding pressing, the crystal grain defect such as to lack, and crystal grain is grown up, and crystal grain performance is improved.Annealing operation is changed to anatase octahedrite unformed non-crystalline state.
The present invention adopts anodic oxidation, electrocorrosion in the glycerine solution of containing sodium fluoride (Neutral ammonium fluoride), improves Nano tube array of titanium dioxide surface flatness.Adopt repeatedly anodic oxidation membrane removal process in early stage, improve the nano-tube array degree of order.Directly by the anodic oxidation of regulating voltage substep, prepare branch type nano-tube array, technique is simple, and preparation cost is low, the appearance structure of flexible modulation nano-tube array.The Nano tube array of titanium dioxide generated for anodic oxidation can not belong to existing brookite, the theory of the titanium dioxide of anatase octahedrite or rutile-type, and the present invention changes into the titanium dioxide of anatase octahedrite or rutile-type by the method for calcining.
The present invention compared with prior art, because the titanium dioxide that the present invention is made is hollow, fills various semi-conductor or conductor material, prepares the PN junction of semi-conductor in emptying aperture, forms diode or triode array.The semiconducting behavior prepared than the also close contact that adulterated by N-type doping and P type is more excellent, also can fill capacitative materials, prepare ultracapacitor.
Accompanying drawing explanation
Fig. 1 is process flow sheet of the present invention.
Fig. 2 is the scanning electron microscope (SEM) photograph of the made branch type nanotube of embodiment 1.
Fig. 3 is the x-ray diffraction pattern of the made branch type nanotube of embodiment 1.
Embodiment:
Below in conjunction with embodiment, the present invention is described in detail.
Embodiment 1:
As shown in Figure 1, a kind of preparation method of branch type Nano tube array of titanium dioxide, comprises the following steps: pretreatment process, anodic oxidation operation.
Described pretreatment process comprises successively:
1) high temperature annealing operation: after titanium sheet being cleaned in ethanol, dries, then puts into retort furnace, spends with 5 degrees/min of temperature programmings to 450, and insulation 4h, is chilled to room temperature naturally with stove;
2) ultrasonic cleaning operation: the titanium sheet that high temperature annealing is good to be placed in ethanolic soln (ethanol: the volume ratio of deionized water is 1:1) ultrasonic vibration 10min in ultrasonic bath, then clean, air-dry stand-by by washed with de-ionized water;
3) chemical rightenning operation: when room temperature, by the titanium sheet of above-mentioned ultrasonic cleaning, is placed in the hydrofluoric acid solution of 0.01mol/L, soaks 5 minutes, uses deionized water rinsing immediately, be transferred to oxidation trough after polishing is complete;
Described anodic oxidation operation comprises the following steps:
4) an anodic oxidation operation: under room temperature, make negative electrode with graphite flake, the titanium sheet that electrochemical etching is good is anode, and at the glycerine solution Anodic Oxidation 1 containing 0.1wt% Sodium Fluoride, voltage is 30V;
5) except anodic oxidation membrane process: by titanium sheet good for an anodic oxidation in containing the phosphoric acid of mass concentration 6% and the chromic acid mixing solutions water-bath 3h of mass concentration 1% respectively, temperature is 40 degree;
6) two-step anodization operation: at the glycerine solution Anodic Oxidation 1h containing 0.1wt% Sodium Fluoride under room temperature, voltage is 30V; Regulating voltage is original
(21.2V) continue anodic oxidation 1 hour, be placed in deionized water and soak, rinse dry;
7) annealing operation: the titanium sheet handled well by two-step anodization puts into retort furnace, 300 degree are carried out anneal, heat-up rate 5 degrees/min, and constant temperature 1h, is cooled to room temperature.
Embodiment 2:
A preparation method for Nano tube array of titanium dioxide, comprises the following steps: pretreatment process, anodic oxidation operation.
Described pretreatment process comprises successively:
1) high temperature annealing operation: after titanium sheet being cleaned in ethanol, dries, then puts into retort furnace, spends with 10 degrees/min of temperature programmings to 500, and insulation 5h, is chilled to room temperature naturally with stove;
2) ultrasonic cleaning operation: the titanium sheet that high temperature annealing is good to be placed in ethanolic soln (ethanol: the volume ratio of deionized water is 1:1.5) ultrasonic vibration 15min in ultrasonic bath, then clean, air-dry stand-by by washed with de-ionized water;
3) chemical rightenning operation: when room temperature, by the titanium sheet of above-mentioned ultrasonic cleaning, is placed in the hydrofluoric acid solution of 0.025mol/L, soaks 10 minutes, uses deionized water rinsing immediately, be transferred to oxidation trough after polishing is complete;
Described anodic oxidation operation comprises the following steps:
4) an anodic oxidation operation: under room temperature, make negative electrode with graphite flake, the titanium sheet that electrochemical etching is good is anode, and at the glycerine solution Anodic Oxidation 2h containing 0.2wt% Neutral ammonium fluoride, voltage is 49V;
5) except anodic oxidation membrane process: by titanium sheet good for an anodic oxidation in containing the phosphoric acid of mass concentration 8% and the chromic acid mixing solutions water-bath 7h of mass concentration 3% respectively, temperature is 60 degree;
6) two-step anodization operation: at the glycerine solution Anodic Oxidation 2h containing 0.2wt% Neutral ammonium fluoride under room temperature, voltage is 49V; Regulating voltage is original
(34.65V) continue anodic oxidation 2 hours, be placed in deionized water and soak, rinse dry;
7) annealing operation: the titanium sheet handled well by two-step anodization puts into retort furnace, 400 degree are carried out anneal, heat-up rate 10 degrees/min, and constant temperature 3h, is cooled to room temperature.
Embodiment 3:
A preparation method for Nano tube array of titanium dioxide, comprises the following steps: pretreatment process, anodic oxidation operation.
Described pretreatment process comprises successively:
1) high temperature annealing operation: after titanium sheet being cleaned in ethanol, dries, then puts into retort furnace, spends with 15 degrees/min of temperature programmings to 530, and insulation 6h, is chilled to room temperature naturally with stove;
2) ultrasonic cleaning operation: the titanium sheet that high temperature annealing is good to be placed in ethanolic soln (ethanol: the volume ratio of deionized water is 1:2) ultrasonic vibration 20min in ultrasonic bath, then clean, air-dry stand-by by washed with de-ionized water;
3) chemical rightenning operation: when room temperature, by the titanium sheet of above-mentioned ultrasonic cleaning, is placed in the hydrofluoric acid solution of 0.05mol/L, soaks 15 minutes, uses deionized water rinsing immediately, be transferred to oxidation trough after polishing is complete;
Described anodic oxidation operation comprises the following steps:
4) an anodic oxidation operation: under room temperature, make negative electrode with graphite flake, the titanium sheet that electrochemical etching is good is anode, and at the glycerine solution Anodic Oxidation 3h containing 0.3wt% Sodium Fluoride, voltage is 60V;
5) except anodic oxidation membrane process: by titanium sheet good for an anodic oxidation in containing the phosphoric acid of mass concentration 10% and the chromic acid mixing solutions water-bath 10h of mass concentration 5% respectively, temperature is 480 degree;
6) two-step anodization operation: at the glycerine solution Anodic Oxidation 3h containing 0.3wt% Sodium Fluoride under room temperature, voltage is 60V; Regulating voltage is original
(42.4V) continue anodic oxidation 3 hours, be placed in deionized water and soak, rinse dry;
7) annealing operation: the titanium sheet handled well by two-step anodization puts into retort furnace, 500 degree are carried out anneal, heat-up rate 20 degrees/min, and constant temperature 4h, is cooled to room temperature.
The pattern scanning electron microscope (SEM) photograph as shown in Figure 2 of the titanium dioxide that embodiment 1 is made, as shown in Figure 3: the made nanotube of embodiment 1 has the diffraction peak of anatase titania and the diffraction peak of titanium substrate.
Embodiment 4: branch type nanotube galvanic deposit ruthenium oxide hydration made for embodiment 1 is prepared ultracapacitor, comprises the following steps:
Get a branch type titania nanotube, be placed in the composite plating solution be made up of the chloride hydrate ruthenium of 5mM, the hydrochloric acid of 0.01M and the Repone K of 0.1M, heating makes temperature of electroplating solution remain 50 degree, keeps the stirring velocity of 20-30 rev/min, in-0.1 ~ 1V potential range, with 0.1Vs
-1sweep velocity carry out cyclic voltammetry scan.Treat that electrode face is brown, show that ruthenium oxide hydration is successfully electroplated and be packed in nanotube, take out electrode, rinsed clean also dries.
In order to measure capacitive property, with saturated Repone K for electrolytic solution, cyclic voltammetry being carried out to the nanotube of filling before and after ruthenium oxide hydration and compares.Find that the area ratio electric capacity after plating ruthenium oxide hydration is 3.64 × 10
-3fcm
-2, and the electric capacity do not electroplated is only 4.48 × 10
-5fcm
-2, large two orders of magnitude, illustrate that this kind of method is applicable to preparing the electrical condenser of ruthenium oxide hydration material very much.
Claims (4)
1. a preparation method for branch type Nano tube array of titanium dioxide, comprises the following steps: pretreatment process, anodic oxidation operation, annealing operation.
2. the preparation method of a kind of branch type Nano tube array of titanium dioxide according to claim 1, is characterized in that:
Described pretreatment process comprises successively:
1) high temperature annealing operation: after titanium sheet being cleaned in ethanol, dries, then puts into retort furnace, and with 5-15 degree/min of temperature programming to 450-530 degree, insulation 4-6h, is chilled to room temperature naturally with stove;
2) ultrasonic cleaning operation: the titanium sheet that high temperature annealing is good to be placed in ethanolic soln (ethanol: the volume ratio of deionized water is 1:1-2) ultrasonic vibration 10-20min in ultrasonic bath, then clean, air-dry stand-by by washed with de-ionized water;
3) chemical rightenning operation: when room temperature, by the titanium sheet of above-mentioned ultrasonic cleaning, is placed in the hydrofluoric acid solution of 0.01-0.05mol/L, soaks 5-20 minute, uses deionized water rinsing immediately, be transferred to oxidation trough after polishing is complete.
3. the preparation method of a kind of branch type Nano tube array of titanium dioxide according to claim 1, is characterized in that:
Described anodic oxidation operation comprises the following steps successively:
4) an anodic oxidation operation: under room temperature, make negative electrode with graphite flake, the titanium sheet that electrochemical etching is good is anode, and at the glycerine solution Anodic Oxidation 1-3h containing 0.1-0.3wt% Sodium Fluoride (Neutral ammonium fluoride), voltage is 30-60V;
5) except anodic oxidation membrane process: by titanium sheet good for an anodic oxidation in containing the phosphoric acid of mass concentration 6-10% and the chromic acid mixing solutions water-bath 3-10h of mass concentration 1-5% respectively, temperature is 40-80 degree;
6) two-step anodization operation: at the glycerine solution Anodic Oxidation 1-3h containing 0.1-0.3wt% Sodium Fluoride (Neutral ammonium fluoride) under room temperature, voltage is 30-60V; Regulating voltage is original
continue anodic oxidation 1-3 hour, be placed in deionized water and soak, rinse dry.
4. the preparation method of a kind of branch type Nano tube array of titanium dioxide according to claim 1, is characterized in that:
Described annealing operation is:
7) annealing operation: the titanium sheet handled well by two-step anodization puts into retort furnace, 300-500 degree carries out anneal, heat-up rate 5-20 degree/min, and constant temperature 1-4h, is cooled to room temperature.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106978619A (en) * | 2017-04-10 | 2017-07-25 | 四川理工学院 | A kind of enhancing titania nanotube is to visible light-responded preparation method |
| CN108439546A (en) * | 2018-03-01 | 2018-08-24 | 南京大学 | Auto-dope TiO2Nanotube electrode, preparation method and applications |
Citations (2)
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| CN101660189A (en) * | 2008-08-28 | 2010-03-03 | 中国科学院合肥物质科学研究院 | Branch controllable titanium dioxide nanotube array film and preparation method thereof |
| CN101748463A (en) * | 2008-12-02 | 2010-06-23 | 中国科学院兰州化学物理研究所 | Method for preparing porous titanium dioxide nanotube array |
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2015
- 2015-10-28 CN CN201510726449.0A patent/CN105369323A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101660189A (en) * | 2008-08-28 | 2010-03-03 | 中国科学院合肥物质科学研究院 | Branch controllable titanium dioxide nanotube array film and preparation method thereof |
| CN101748463A (en) * | 2008-12-02 | 2010-06-23 | 中国科学院兰州化学物理研究所 | Method for preparing porous titanium dioxide nanotube array |
Non-Patent Citations (3)
| Title |
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| BO CHEN: "Hierarchically Branched Titania Nanotubes with Tailored Diameters and Branch Numbers", 《LANGMUIR 》 * |
| 张世英: "《一维氧化钛纳米材料》", 30 September 2015, 长沙：中南大学出版社 * |
| 杜力: "《机械工程材料》", 31 January 2014, 北京：机械工业出版社 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106978619A (en) * | 2017-04-10 | 2017-07-25 | 四川理工学院 | A kind of enhancing titania nanotube is to visible light-responded preparation method |
| CN108439546A (en) * | 2018-03-01 | 2018-08-24 | 南京大学 | Auto-dope TiO2Nanotube electrode, preparation method and applications |
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Application publication date: 20160302 |