CN101260557B - Coaxial double-pipe titanium dioxide nano-pipe array thin film and preparation method thereof - Google Patents
Coaxial double-pipe titanium dioxide nano-pipe array thin film and preparation method thereof Download PDFInfo
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Abstract
The invention provides a coaxial double-pipe titania nano pipe array membrane and a preparation method for the coaxial double-pipe titania nano pipe array membrane. The invention is characterized in that: the coaxial nano pipe array consists of the following chemical compositions by weight percent: 6.97 to 9.07 percent of niobium, 2.08 to 2.25 percent of molybdenum, 0.35 to 0.82 percent of zirconium, 48.49 to 49.35 percent of oxygen, residual titanium and other unavoidable impurities. The coaxial double-pipe titania nano pipe array membrane has unique coaxial nano pipe structural characteristics and obvious semiconductor comprehensive performances and particularly has good photocatalysis performance; moreover, the membrane has high biological activity and can be mainly applied in the photocatalysis and tissue engineering field; simultaneously, the membrane can be widely applied in the fields such as solar batteries, filtration and separation, sensors, micro-nano devices, optical devices and so on.
Description
Technical field
The invention belongs to the inorganic semiconductor technical field of nano material, relate to a kind of coaxial double-pipe titanium dioxide nano-pipe array thin film and preparation method thereof.
Background technology
TiO
2Have good photolytic activity, biocompatibility, weathering resistance, higher chemical stability, thermostability; And nontoxicity, non-corrosiveness etc. become one of research focus of field of functional materials.Because nano-TiO
2Have very high surface-area, more excellent thing, voltinism energy, its potential Application Areas is also more wide, and at present, many scientific research institutions have carried out its applied research in fields such as the energy, environment protection and bioengineered tissues.
Nano-TiO
2As functional materials many kinds of existence forms, for example nano thin-film, nano particle, nano wire etc. are arranged.The purpose for preparing these multi-form nanostructures is to promote its functional performance as wide as possible, for example by increasing specific surface area, widens light absorbing range of frequency, improves charge-conduction ability or the like, thereby improves the application performance of TiOx.This just impels more nanometer structure formations constantly to occur.The nano-tube array that wherein has the high-sequential structure has caused scholars' extensive interest.TiO
2Nano-pipe array thin film and powder nano-TiO
2Film is compared has bigger specific surface area and stronger adsorptive power.Simultaneously, because TiO
2The oldered array structure formation that nano tube structure had can improve the transmission life-span of photogenerated charge and reduce its recombination probability after using this material.Therefore this material can be used for fields such as high sensor, dye sensitization solar battery, photolysis water hydrogen gas.TiO at room temperature for example
2Nano-tube array can be tested the hydrogen content (TiO behind the chemisorption hydrogen of 1000ppm
2Nano-tube film resistance increases by 8 orders of magnitude), this is the material the most responsive to hydrogen known at present.Except the hydrogen sensing characteristics, nano-tube array also has outstanding photoelectric characteristic.Under the irradiation of UV-light, this material can carry out automatically cleaning, and nearest applied research also comprises, dye sensitization solar battery.The orientation growths of the arrangement by control nanometer pore, crystallization, nanotube etc. make nanotube have excellent electron-osmosis transmission path between the interface, utilize this class TiO
2Dye sensitization solar battery system electricity conversion under the AM1.5 condition of nano-pipe array thin film assembling has reached 5.44%; High-sequential TiO
2Nanotube also has significant photolysis water characteristic, and (under 320～400nm) irradiations, length reaches 16.25% at the electricity conversion of more than 30 microns nano-tube array in UV-light.In addition, because this material has the ordered nano pore structure of marshalling.Therefore can also be applied to high-tech sectors such as microfluidic control, molecular filtration, drug conveying and bioengineered tissue.
In recent years, improve the performance of material by the control of nanostructure, be the focus of nanosecond science and technology worker research always.For example, the semiconductor nano concentric cable is exactly one of them, and this material is a kind of nano wire with multilayered structure, and likeness in form is used for the concentric cable of cable TV network, but its diameter have only 100,000 of concentric cable/.Utilize the nano coaxial cable technology, be expected to develop the solar cell that performance is greatly improved.The relevant expert points out that the nano coaxial cable technology will be found broad application at microelectronic equally, also can be used for developing nanocomputer.At present, about TiO
2The tubular construction control of nano-tube array, people have also done a large amount of research, for example by the control of electrochemical parameter, the nanotube internal diameter can be controlled in 10～150nm scope, and tube wall is in 4～50nm scope, and nanotube length is up to 300 microns.But Shang Weijian has the nano-tube array structure report of coaxial or other heterojunction structure.Therefore, research and development are expected to present more high performance TiO
2Heterogeneous nano tube structure has become TiO
2The important development direction of nanotube preparation research.
Summary of the invention
The objective of the invention is to provides a kind of coaxial double-pipe titanium dioxide nano-pipe array thin film and preparation method thereof at the deficiencies in the prior art.This preparation method can realize successfully that the preparation of nano tube structure and element doping carry out synchronously.
To achieve these goals, the technical solution used in the present invention is: a kind of coaxial double-pipe titanium dioxide nano-pipe array thin film is characterized in that this co-axial nano pipe array is made up of the chemical ingredients of following weight percent:
Nb 6.97～9.07%, and Mo 2.08～2.25%, and Zr 0.35～0.82%, and O 48.49～49.35%, and all the other are Ti and unavoidable impurities.
Another object of the present invention provides a kind of preparation method of coaxial double-pipe titanium dioxide nano-pipe array thin film, it is characterized in that this method may further comprise the steps:
(1) the TLM titanium-alloy thin-plate is before anodic oxidation, carry out following pre-treatment: the sheet that is machined into 10～200mm * 100～500mm, behind 150#, 600#, 1000# sand papering light, ultrasonic oil removing in ethanol, acetone successively, use washed with de-ionized water, dry in 70 ℃～80 ℃ hot-air ovens, stand-by; Described TLM titanium-alloy thin-plate is the Ti-Zr-Mo-Nb-Sn thin plate;
(2) carry out anodic oxidation through pretreated TLM substrate, used electrolytic solution is for containing 0.2～1.0wt%NH
4F, 0.5～2.0wt%H
2The ethylene glycol solution of O;
(3) the TLM substrate is an anode, is negative electrode with the platinized platinum, under the magneton whipped state, carries out electrochemical reaction during room temperature, and its interelectrode distance 50mm, voltage be at 30～80V, anodizing time 4～24 hours;
(4) will repeatedly clean with deionized water by the nano-tube array of anodic oxidation preparation, place loft drier, dried 1 hour for 70 ℃～80 ℃, obtain nano-pipe array thin film;
(5) nano-pipe array thin film that step (4) is obtained is taken off from matrix, be fixed on the PVC plate of hollow, subsequently the PVC plate is placed on the plastics spout that fills saturated HF acid, the bottom surface of nano-tube array is in the HF acid gas atmosphere, utilize HF gas to remove the nano-pipe array thin film back of the body blocking layer at the end, promptly obtain two-tube co-axial nano pipe array film;
(6) the two-tube co-axial nano pipe array film that step (5) is obtained carries out anneal in retort furnace, 1 ℃/min of control temperature rate, 400 ℃～700 ℃ of flat-temperature zone scopes, constant temperature 120～480 minutes.
The coaxial TiO of the element dopings such as Nb that the present invention is prepared
2The nano-pipe array thin film essential characteristic is: film thickness is at 0.5～320 μ m, and the inside and outside diameter range of outer tube is respectively at 80～260nm, 110～280nm, and the inside and outside diameter range of interior pipe is respectively at 50～210nm, 70～250nm; Tube spacing is at 10～50nm, and outer tube slightly is longer than interior pipe.
The present invention compared with prior art has the following advantages: the present invention has unique co-axial nano tubular construction feature and significant semi-conductor over-all properties, especially has excellent photocatalytic performance, and have higher biological activity, but emphasis is applied in photochemical catalysis, field of tissue engineering technology; Simultaneously, the present invention can also be widely used in fields such as solar cell, filtering separation, transmitter, micro-nano device, optics.
Description of drawings
Fig. 1 is impressed voltage 50V, at 0.25wt%NH
4F, 1.0wt%H
2In the ethylene glycol solution of O, the coaxial TiO of the element dopings such as Nb that anodic oxidation 4320min is prepared
2The FE-SEM figure of nano-pipe array thin film: (a) blocking layer is removed in bottom surface, bottom surface, upper surface (b) cross section (c) (d).
Fig. 2 is impressed voltage 40V, at 0.5wt%NH
4F, 1.0wt%H
2In the ethylene glycol solution of O, the coaxial TiO of element dopings such as the prepared Nb of anodic oxidation 2100min
2The FE-SEM figure of nano-pipe array thin film: (a) bottom surface, cross section (b).
Fig. 3 is impressed voltage 50V, at 0.25wt%NH
4F, 1.0wt%H
2In the ethylene glycol solution of O, the coaxial TiO of element dopings such as the prepared Nb of anodic oxidation 480min
2The EDS of nano-pipe array thin film can spectrogram.
Fig. 4 is impressed voltage 50V, at 0.25wt%NH
4F, 1.0wt%H
2In the ethylene glycol solution of O, the coaxial TiO of element dopings such as the prepared Nb of anodic oxidation 4320min
2Nano-pipe array thin film is through 500 ℃, insulation 120min annealed X-ray diffractogram.
Fig. 5 is impressed voltage 60V, at 0.2wt%NH
4F, 1.0wt%H
2In the ethylene glycol solution of O, the coaxial TiO of element dopings such as the prepared Nb of anodic oxidation 4320min
2Nano-pipe array thin film is through 500 ℃ of insulation 240min annealed ultraviolet-visible light photoabsorption figure.
Fig. 6 be the nano-tube array that obtains of pure Ti, the self-assembly of TLM alloy surface in 1molNaOH solution after the pre-treatment, two kinds of biomaterial surface Oesteoblast growth effects.
Embodiment
The TLM thin plate is machined into the sheet of 500mm * 100mm * 1mm, and behind 150#, 600#, 1000# sand papering light, washed with de-ionized water is used in ultrasonic oil removing in ethanol, acetone successively, dries in 70 ℃～80 ℃ hot-air ovens; Impressed voltage 50V is at 0.25wt%NH
4F, 1.0wt%H
2In the ethylene glycol solution of O, anodic oxidation 4320min obtains nano-tube array.Nano-tube array repeatedly cleans with deionized water, places loft drier, dries 1 hour for 70 ℃～80 ℃.Then, with the nano-pipe array thin film that obtains.The nano-pipe array thin film that obtains is taken off from matrix, be fixed on the PVC plate of hollow, PVC is placed on the plastics spout that fills saturated HF acid subsequently, the bottom surface of nano-tube array is in the HF acid gas atmosphere, utilize HF gas to remove the nano-pipe array thin film back of the body blocking layer at the end, adopt the FE-SEM figure of the nano-tube array of this prepared, as shown in Figure 1.
The coaxial TiO of the element dopings such as Nb that present embodiment is prepared
2Nano-tube array has good comprehensive performances, especially has good ultraviolet absorption performance.
The TLM thin plate is machined into the sheet of 300mm * 20mm * 1mm, and behind 150#, 600#, 1000# sand papering light, washed with de-ionized water is used in ultrasonic oil removing in ethanol, acetone successively, dries in 70 ℃～80 ℃ hot-air ovens; Impressed voltage 40V is at 0.25wt%NH
4F, 1.0wt%H
2In the ethylene glycol solution of O, the coaxial TiO of the element dopings such as Nb that anodic oxidation 480min is prepared
2Nano-tube array.Nano-tube array repeatedly cleans with deionized water, places loft drier, dries 1 hour for 70 ℃～80 ℃.Adopt the EDS of the nano-pipe array thin film of this prepared can spectrogram as shown in Figure 3.
Present embodiment is at the coaxial TiO of the prepared element dopings such as Nb of TLM alloy surface
2Nano-pipe array thin film, can improve scleroblast in the growth of TLM alloy surface, seek connections with ability.Compare coaxial TiO with Ti alloy surface nano-tube array
2Nano-pipe array thin film surface Oesteoblast growth is more effective, as shown in Figure 6.
Embodiment 3
The TLM thin plate is machined into the sheet of 300mm * 20mm * 1mm, and behind 150#, 600#, 1000# sand papering light, washed with de-ionized water is used in ultrasonic oil removing in ethanol, acetone successively, dries in 70 ℃～80 ℃ hot-air ovens; Impressed voltage 50V is at 0.25wt%NH
4F, 1.0wt%H
2In the ethylene glycol solution of O, the co-axial nano pipe array film that anodic oxidation 4320min is prepared.Nano-pipe array thin film repeatedly cleans with deionized water, places loft drier, dries 1 hour for 70 ℃～80 ℃.Sample has in the oxygen atmosphere in retort furnace anneals, 1 ℃/min of control temperature rate, 500 ℃ of constant temperature points, insulation 120min.Adopt this prepared nano-tube array X-ray diffractogram as shown in Figure 4.
Embodiment 4
The TLM thin plate is machined into the sheet of 100mm * 30mm * 1mm, and behind 150#, 600#, 1000# sand papering light, washed with de-ionized water is used in ultrasonic oil removing in ethanol, acetone successively, dries in 70 ℃～80 ℃ hot-air ovens; Impressed voltage 60V is at 0.2wt%NH
4F, 1.0wt%H
2In the ethylene glycol solution of O, the co-axial nano pipe array that anodic oxidation 720min is prepared.Nano-tube array repeatedly cleans with deionized water, places loft drier, dries 1 hour for 70 ℃～80 ℃.The nano-pipe array thin film that obtains is taken off from matrix, be fixed on the PVC plate of hollow, PVC is placed on the plastics spout that fills saturated HF acid subsequently, the bottom surface of nano-tube array is in the HF acid gas atmosphere, utilize HF gas to remove the nano-pipe array thin film back of the body blocking layer at the end, obtain bilateral co-axial nano pipe array film.
Embodiment 5
The TLM thin plate is machined into the sheet of 500mm * 100mm * 1mm, and behind 150#, 600#, 1000# sand papering light, washed with de-ionized water is used in ultrasonic oil removing in ethanol, acetone successively, dries in 70 ℃～80 ℃ hot-air ovens; Impressed voltage 40V is at 0.5wt%NH
4F, 1.0wt%H
2In the ethylene glycol solution of O, the coaxial TiO that anodic oxidation 1200min is prepared
2Nano-pipe array thin film.Nano-pipe array thin film repeatedly cleans with deionized water, places loft drier, dries 1 hour for 70 ℃～80 ℃.Film thickness is at 36 μ m, and the inside and outside diameter range of outer tube is respectively at 110nm, 130nm, and the inside and outside diameter range of interior pipe is respectively at 50nm, 80～100nm, and interior pipe progressively reduces from the bottom to the top, tapered structure; Tube spacing is at 10～30nm.
Claims (1)
1. coaxial double-pipe titanium dioxide nano-pipe array thin film is characterized in that this co-axial nano pipe array is made up of the chemical ingredients of following weight percent:
Nb 6.97～9.07%, and Mo 2.08～2.25%, and Zr 0.35～0.82%, and O 48.49～49.35%, and all the other are Ti and unavoidable impurities; The preparation method of this co-axial nano pipe array film may further comprise the steps:
(1) the TLM titanium-alloy thin-plate is before anodic oxidation, carry out following pre-treatment: the sheet that is machined into 10～200mm * 100～500mm, behind 150#, 600#, 1000# sand papering light, ultrasonic oil removing in ethanol, acetone successively, use washed with de-ionized water, dry in 70 ℃～80 ℃ hot-air ovens, stand-by; Described TLM titanium-alloy thin-plate is the Ti-Zr-Mo-Nb-Sn thin plate;
(2) carry out anodic oxidation through pretreated TLM substrate, used electrolytic solution is for containing 0.2～1.0wt%NH
4F, 0.5～2.0wt%H
2The ethylene glycol solution of O;
(3) the TLM substrate is an anode, is negative electrode with the platinized platinum, under the magneton whipped state, carries out electrochemical reaction during room temperature, and its interelectrode distance 50mm, voltage be at 30～80V, anodizing time 4～24 hours;
(4) will repeatedly clean with deionized water by the nano-tube array of anodic oxidation preparation, place loft drier, dried 1 hour for 70 ℃～80 ℃, obtain nano-pipe array thin film;
(5) nano-pipe array thin film that step (4) is obtained is taken off from matrix, be fixed on the PVC plate of hollow, subsequently the PVC plate is placed on the plastics spout that fills saturated HF acid, the bottom surface of nano-tube array is in the HF acid gas atmosphere, utilize HF gas to remove the nano-pipe array thin film back of the body blocking layer at the end, promptly obtain two-tube co-axial nano pipe array film;
(6) the two-tube co-axial nano pipe array film that step (5) is obtained carries out anneal in retort furnace, 1 ℃/min of control temperature rate, 400 ℃～700 ℃ of flat-temperature zone scopes, constant temperature 120～480 minutes.
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| US8920767B2 (en) | 2011-08-19 | 2014-12-30 | Ut-Battelle, Llc | Array of titanium dioxide nanostructures for solar energy utilization |
| CN102534723B (en) * | 2011-11-30 | 2015-03-11 | 景德镇陶瓷学院 | Preparation method for ultrafast anode self-assembly double-pass porous nanometer ternary oxide and products prepared through same and purpose of products |
| CN102703952B (en) * | 2012-05-30 | 2015-08-05 | 四川农业大学 | Utilize ionic liquid on titanium base, prepare method and the application thereof of carbon boron N doping double-pipe titanium dioxide nano-pipe array |
| CN104451824B (en) * | 2014-11-28 | 2017-01-18 | 四川大学 | Method and application of peeling titanium surface coating by adopting nanotube treatment method |
| CN109652838B (en) * | 2018-12-27 | 2021-05-18 | 浙江工业大学 | Titanium-niobium alloy surface anodic oxidation coloring method |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20050224360A1 (en) * | 2004-04-02 | 2005-10-13 | The Penn Research Foundation | Titania nanotube arrays for use as sensors and method of producing |
| CN1884630A (en) * | 2006-06-01 | 2006-12-27 | 厦门大学 | High length-diameter ratio titania nanometer tube array preparation method |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20050224360A1 (en) * | 2004-04-02 | 2005-10-13 | The Penn Research Foundation | Titania nanotube arrays for use as sensors and method of producing |
| CN1884630A (en) * | 2006-06-01 | 2006-12-27 | 厦门大学 | High length-diameter ratio titania nanometer tube array preparation method |
Non-Patent Citations (8)
| Title |
|---|
| Haripriya E. Prakasam, Karthik Shankar, Maggie Paulose,Oomman K. Varghese, and Craig A. Grimes.A New Benchmark for TiO2 Nanotube Array Growth byAnodization.JOURNAL OF PHYSICAL CHEMISTRY C111 20.2007,111(20),7235-7241. |
| Haripriya E. Prakasam, Karthik Shankar, Maggie Paulose,Oomman K. Varghese, and Craig A. Grimes.A New Benchmark for TiO2 Nanotube Array Growth byAnodization.JOURNAL OF PHYSICAL CHEMISTRY C111 20.2007,111(20),7235-7241. * |
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| Paulose, M;Shankar, K;Yoriya, S, et al..Anodic growth of highly ordered TiO2 nanotube arrays to 134mu m in length.JOURNAL OF PHYSICAL CHEMISTRY B110 33.2006,110(33),16179-16184. * |
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