CN102191529B - Honeycomb ordered titanium dioxide nanotube array film and preparation method thereof - Google Patents
Honeycomb ordered titanium dioxide nanotube array film and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a honeycomb ordered titanium dioxide nanotube array film and a preparation method thereof. The honeycomb ordered titanium dioxide nanotube array film consists of an upper-layer ordered structure and a lower-layer ordered structure, namely an upper-layer large-diameter regular hexagonal titanium dioxide nanopore array and a lower-layer small-diameter titanium dioxide nanotube array, wherein a low-layer nanotube orifice end is positioned in upper-layer titanium dioxide nanopores and the upper-layer nanopores are communicated so as to form a honeycomb structure. The method is easy to operate, equipment is cheap, and parameters of the structure can be effectively controlled by changing the oxidation voltage and the oxidation time of an anode; moreover, titanium dioxide with the hierarchical structure can be widely applied to dye-sensitized solar cells, gas sensors, hydrogen preparation from water by photodecomposition, and photonic crystals.
Description
Technical field
The present invention relates to a kind of pervasive electrochemistry anodic oxidation, the nanometer titania nano-tube array for the preparation of a kind of novel classification is specifically related to film of Nano tube array of titanium dioxide of a kind of honeycomb-patterned ordered and preparation method thereof.
Background technology
Pure titanium sheet (is mainly the organic or inorganic ionogen of fluoride ion) in some dielectric medium, can obtain the Nano tube array of titanium dioxide of ordered arrangement by anodic oxidation.These are by the Nano tube array of titanium dioxide of anonizing preparation, because of its unique tubular structure, high specific surface area and orderly arrangement mode, it are being had broad application prospects at environment, the energy, biology and optical field.In recent years, people mainly comprise the relation between oxidation voltage, oxidization time and electrolyte ingredient and concentration and titanium dioxide caliber, the pipe range always in the relation of seeking untiringly between electrochemical anodic oxidation parameter and the Nano tube array of titanium dioxide pattern.Yet used these work all concentrate on straight Nano tube array of titanium dioxide, the titania nanotube that namely all equates to the diameter of managing the bottom from the pipe top.Along with the development of nano science, this Nano tube array of titanium dioxide that only has single diameter perhaps can not satisfy the application demand of reality fully.Therefore probe into a kind of easy, effective synthetic method, the preparation complex structure, the controlled Novel Titanium dioxide nanotube of parameter is with significant.
Summary of the invention
It is cheap that the present invention is intended to develop a kind of equipment, and the simple efficient synthesis of working method is constructed for the preparation of the novel nano structure titanium dioxide that structural parameter are controlled.
The present invention adopts following technical scheme to achieve these goals:
The film of Nano tube array of titanium dioxide of honeycomb-patterned ordered is characterized in that:
The film of Nano tube array of titanium dioxide of described honeycomb-patterned ordered is comprised of upper and lower two-layer titanium dioxide nano-pore, and is supported on the titanium sheet substrate;
Described upper strata titanium dioxide nano-pore is orderly regular hexagon array, and its aperture is 70-250nm;
Described lower floor titanium dioxide nano-pore is real to be titania nanotube, and its opening end is to be arranged in the upper strata nanoporous, and each tube opening end is bonded to each other in the axial direction, and the aperture in lower floor hole is 15-40nm, and the degree of depth is 100-2000nm.
The preparation method of the film of Nano tube array of titanium dioxide of described honeycomb-patterned ordered is characterized in that may further comprise the steps:
(1) at first pure titanium sheet is put into that ultrasonic cleaning 55-65min removes the organism on surface in the mixing solutions of ethanol and acetone, and then repeatedly cleaned with deionized water, and dry;
(2) the titanium sheet after cleaning is dried is put into the ethylene glycol solution that contains 0.2mol/l hydrofluoric acid and is carried out anodic oxidation, and wherein oxidation voltage is 40-105v, and oxidization time is 1.2-1.5h, and titanium plate surface forms Nano tube array of titanium dioxide;
(3) will take out at the titanium sheet of hydrofluoric acid ethylene glycol ionogen Anodic Oxidation, place dehydrated alcohol, and by sonic oscillation, so that the Nano tube array of titanium dioxide of titanium plate surface is removed, stay the circular titanium dioxide nano-pore of ordered arrangement at titanium sheet substrate;
(4) preparation contains the ethylene glycol ionogen of 0.26mol/l Neutral ammonium fluoride, and will put into this ionogen through the titanium sheet after step (3) processing and carry out the anodic oxidation second time, its oxidation voltage is 15-30v, oxidization time is 10-70min, generate the more Nano tube array of titanium dioxide of minor diameter in the circular titanium dioxide nano-pore that this anode oxidation process can obtain in step (3), the circular titanium dioxide nano-pore enlarged-diameter that obtains in the step (3) simultaneously, and circular port is transformed into the regular hexagon hole, thereby forms the honeycomb-patterned ordered film of Nano tube array of titanium dioxide at the titanium sheet.
The preparation method of described honeycomb-patterned ordered film of Nano tube array of titanium dioxide is characterized in that: obtain by titanium sheet two-step electrochemical anodic oxidation treatment in the ethylene glycol organic electrolyte solution of hydrofluoric acid containing, Neutral ammonium fluoride.
The preparation method of described honeycomb-patterned ordered Nano tube array of titanium dioxide, it is characterized in that: by changing an anodic oxidation voltage from 40-105v, can make the Nano tube array of titanium dioxide of 50-120nm diameter range, after the ultrasonic vibration processing, can obtain diameter range at the circular titanium dioxide nano-pore array of 60-180nm.
The preparation method of described honeycomb-patterned ordered film of Nano tube array of titanium dioxide, it is characterized in that: during two-step anodization voltage, by changing oxidation voltage from 15-30v, make the Nano tube array of titanium dioxide of 15-40nm diameter range in can the nanohole array after once oxidation is processed, obtain circular nanoporous enlarged-diameter after the simultaneously anodic oxidation to 70-250nm, and circular port is transformed into the regular hexagon hole, thereby forms the honeycomb-patterned ordered film of Nano tube array of titanium dioxide.
The preparation method of described honeycomb-patterned ordered film of Nano tube array of titanium dioxide, it is characterized in that: when two-step anodization voltage, by changing oxidization time from 10-70min, can control secondary oxidation and make titania nanotube length between 100-2000nm.
In fact, the present invention adopts simple electrochemical apparatus, in conjunction with cheap electrochemical anodic oxidation technology, synthesized at ambient temperature the controlled cellular titania nanotube oldered array film of structural parameter, this structure is assembled by the titania nanotube of different tube diameters, prepare the honeycomb-patterned ordered titanium dioxide nano material with this method, can by changing anodic oxidation voltage, reach the parameter that oxidization time just can be controlled this structure effectively.
Beneficial effect of the present invention:
The present invention adopts simple electrochemical apparatus, in conjunction with cheap electrochemical anodic oxidation technology, synthesized at ambient temperature by titania nanotube and consisted of the nano-porous films that honeycomb-patterned ordered is arranged, and this novel nano structure to have size controlled; Institute's employing method is simple to operate, equipment is cheap, can pass through to change electrolyte ingredient or concentration, and by changing anodic oxidation voltage, oxidization time, just can effectively control the parameter of this structure; This hierarchy titanium dioxide can be widely used aspect dye sensitization solar battery, gas sensor, photolysis water hydrogen and the photonic crystal.
Description of drawings
Fig. 1 is the process schematic diagram that the present invention prepares the honeycomb-patterned ordered film of Nano tube array of titanium dioxide.
Wherein figure (a) is the Nano tube array of titanium dioxide of anodic oxidation preparation, figure (b) stays the titanium dioxide nano-pore array on the titanium sheet substrate after for the titania nanotube that removes anodic oxidation preparation, and figure (c) be the honeycomb-patterned ordered film of Nano tube array of titanium dioxide for preparing by two-step anodization.
Fig. 2 is that the present invention prepares each process of honeycomb-patterned ordered film of Nano tube array of titanium dioxide corresponding microtexture and characterization result by anodic oxidation.
Figure (a) is the Nano tube array of titanium dioxide of anodic oxidation preparation, figure (b) is the titanium dioxide nano-pore oldered array that stays after the Nano tube array of titanium dioxide that an anodic oxidation generates is removed, figure (c) is the honeycomb-patterned ordered film of Nano tube array of titanium dioxide top SEM figure by the two-step anodization preparation, and figure (d) is the side SEM figure of honeycomb-patterned ordered film of Nano tube array of titanium dioxide.
Fig. 3 is in the hydrofluoric acid ethylene glycol ionogen of 0.2M, behind the titanium dioxide nano-pore array that obtains under the 100v oxidation voltage, at the honeycomb-patterned ordered film of Nano tube array of titanium dioxide that carries out under the different voltages preparing behind the secondary oxidation.
The sample of figure (a) for preparing under the 15v oxidation voltage, wherein hole diameter is 17nm; The sample of figure (b) for preparing under the 20v oxidation voltage, wherein hole diameter is 24nm; The sample of figure (c) for preparing under the 25v oxidation voltage, wherein hole diameter is 31nm; Figure (d) sample for preparing under the 30v oxidation voltage, wherein hole diameter be 39nm. wherein the upper right corner of each figure be the partial enlarged drawing sheet.
Embodiment
The film of Nano tube array of titanium dioxide of embodiment honeycomb-patterned ordered, the titania nanotube shape array films of described honeycomb-patterned ordered is comprised of upper and lower two-layer titanium dioxide nano-pore, and is supported on the titanium sheet substrate;
Described upper strata titanium dioxide nano-pore is orderly regular hexagon array, and its aperture is 70-250nm;
Described lower floor titanium dioxide nano-pore is real to be titania nanotube, and its opening end is to be arranged in the upper strata nanoporous, and each tube opening end is bonded to each other in the axial direction, and the aperture in lower floor hole is 15-40nm, and the degree of depth is 100-2000nm.
The preparation method of the film of Nano tube array of titanium dioxide of honeycomb-patterned ordered may further comprise the steps:
(1) at first pure titanium sheet is put into that ultrasonic cleaning 55-65min removes the organism on surface in the mixing solutions of ethanol and acetone, and then repeatedly cleaned with deionized water, and dry;
(2) the titanium sheet after cleaning is dried is put into the ethylene glycol solution that contains 0.2mol/l hydrofluoric acid and is carried out anodic oxidation, and wherein oxidation voltage is 40-105v, and oxidization time is 1.2-1.5h, and titanium plate surface forms Nano tube array of titanium dioxide;
(3) will take out at the titanium sheet of hydrofluoric acid ethylene glycol ionogen Anodic Oxidation, place dehydrated alcohol, and by sonic oscillation, so that the Nano tube array of titanium dioxide of titanium plate surface is removed, stay the circular titanium dioxide nano-pore of ordered arrangement at titanium sheet substrate;
(4) preparation contains the ethylene glycol ionogen of 0.26mol/l Neutral ammonium fluoride, and will put into this ionogen through the titanium sheet after step (3) processing and carry out the anodic oxidation second time, its oxidation voltage is 15-30v, oxidization time is 10-70min, generate the more Nano tube array of titanium dioxide of minor diameter in the circular titanium dioxide nano-pore that this anode oxidation process can obtain in step (3), the circular titanium dioxide nano-pore enlarged-diameter that obtains in the step (3) simultaneously, and circular port is transformed into the regular hexagon hole, thereby forms the honeycomb-patterned ordered film of Nano tube array of titanium dioxide at the titanium sheet.
Obtain by the twice electrochemical anodic oxidation processing in the ethylene glycol organic electrolyte solution of hydrofluoric acid containing, Neutral ammonium fluoride of titanium sheet.
By changing an anodic oxidation voltage from 40v-105v, can make the Nano tube array of titanium dioxide of 50-120nm scope diameter, after processing by ultrasonic vibration, can obtain diameter range at the titanium dioxide nano-pore array of 60-180nm.
During two-step anodization voltage, by changing oxidation voltage from 15v-30v, make the Nano tube array of titanium dioxide of 15-40nm diameter range in can the nanohole array after once oxidation is processed, obtain circular nanoporous enlarged-diameter to 70-250nm after a simultaneously anodic oxidation and the vibration, and circular port is transformed into the regular hexagon hole, thereby forms the honeycomb-patterned ordered film of Nano tube array of titanium dioxide.
When two-step anodization voltage, by changing oxidization time from 10-70min, can control secondary oxidation and make titania nanotube length between 100-2000nm.
Claims (5)
1. the film of Nano tube array of titanium dioxide of a honeycomb-patterned ordered is characterized in that:
The titania nanotube shape array films of described honeycomb-patterned ordered is comprised of upper and lower two-layer titanium dioxide nano-pore, and is supported on the titanium sheet substrate;
Described upper strata titanium dioxide nano-pore is orderly regular hexagon array, and its aperture is 70-250nm;
Described lower floor titanium dioxide nano-pore is real be titania nanotube, and its opening end is to be arranged in the upper strata nanoporous, and the in the axial direction mutually bonding of each tube opening end, and the aperture in lower floor hole is 15-40nm, and the degree of depth is 100-2000nm;
The preparation method of the film of Nano tube array of titanium dioxide of described honeycomb-patterned ordered may further comprise the steps:
(1) at first pure titanium sheet is put into that ultrasonic cleaning 55-65min removes the organism on surface in the mixing solutions of ethanol and acetone, and then repeatedly cleaned with deionized water, and dry;
(2) the titanium sheet after cleaning is dried is put into the ethylene glycol solution that contains 0.2mol/L hydrofluoric acid and is carried out anodic oxidation, and wherein oxidation voltage is 95-105V, and oxidization time is 1.2-1.5h, and titanium plate surface forms Nano tube array of titanium dioxide;
(3) will take out at the titanium sheet of hydrofluoric acid ethylene glycol ionogen Anodic Oxidation, place dehydrated alcohol, and by sonic oscillation, so that the Nano tube array of titanium dioxide of titanium plate surface is removed, stay the circular titanium dioxide nano-pore of ordered arrangement at titanium sheet substrate;
(4) preparation contains the ethylene glycol ionogen of 0.26mol/L Neutral ammonium fluoride, and will put into this ionogen through the titanium sheet after step (3) processing and carry out the anodic oxidation second time, its oxidation voltage is 15-30V, oxidization time is 10-70min, generate the more Nano tube array of titanium dioxide of minor diameter in the circular titanium dioxide nano-pore that this anode oxidation process can obtain in step (3), the circular titanium dioxide nano-pore enlarged-diameter that obtains in the step (3) simultaneously, and circular port is transformed into the regular hexagon hole, thereby forms the honeycomb-patterned ordered film of Nano tube array of titanium dioxide at the titanium sheet.
2. the film of Nano tube array of titanium dioxide of honeycomb-patterned ordered according to claim 1 is characterized in that: obtain by the twice electrochemical anodic oxidation processing in the ethylene glycol organic electrolyte solution of hydrofluoric acid containing, Neutral ammonium fluoride of titanium sheet.
3. the film of Nano tube array of titanium dioxide of honeycomb-patterned ordered according to claim 1, it is characterized in that: by changing an anodic oxidation voltage from 40V-105V, can make the Nano tube array of titanium dioxide of 50-120nm scope diameter, after the ultrasonic vibration processing, can obtain diameter range at the titanium dioxide nano-pore array of 60-180nm.
4. the film of Nano tube array of titanium dioxide of honeycomb-patterned ordered according to claim 1, it is characterized in that: during two-step anodization voltage, by changing oxidation voltage from 15-30V, make the Nano tube array of titanium dioxide of 15-40nm diameter range in can the nanohole array after once oxidation is processed, obtain circular nanoporous enlarged-diameter to 70-250nm after a simultaneously anodic oxidation and the vibration, and circular port is transformed into the regular hexagon hole, thereby forms the honeycomb-patterned ordered film of Nano tube array of titanium dioxide.
5. the film of Nano tube array of titanium dioxide of honeycomb-patterned ordered according to claim 1, it is characterized in that: when two-step anodization voltage, by changing oxidization time from 10-70min, can control secondary oxidation and make the titania nanotube degree of depth between 100-2000nm.
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|---|---|---|---|---|
| WO2017130029A1 (en) * | 2016-01-29 | 2017-08-03 | Nanoti Limited | Scratch resistance and corrosion behavior of nanotubular and nano-pitted anodic films on medical grade bulk titanium substrates |
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| CN102418133B (en) * | 2011-12-12 | 2014-02-12 | 天津大学 | Nano honeycomb titanium dioxide structure thin film with rough surface and preparation method of nanohoneycomb titanium dioxide structure thin film |
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| CN102776543B (en) * | 2012-05-07 | 2015-07-15 | 中国科学院合肥物质科学研究院 | Preparation method of large-area smooth-surface uncracked anodic oxidation titanium dioxide nanometer tube arrays |
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Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 (2)
| Title |
|---|
| Shiqi Li等.Anodization Fabrication of Highly Ordered TiO2 Nanotubes.《J. Phys. Chem. C》.2009,第113卷12759-12765. * |
| Wang Daoai等.A Novel Protocol Toward Perfect Alignment of Anodized TiO2 Nanotubes.《Advanced Materials》.2009,第21卷1964-1967. * |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2017130029A1 (en) * | 2016-01-29 | 2017-08-03 | Nanoti Limited | Scratch resistance and corrosion behavior of nanotubular and nano-pitted anodic films on medical grade bulk titanium substrates |
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