CN1974405A - Prepn process of periodic nanometer titania line - Google Patents
Prepn process of periodic nanometer titania line Download PDFInfo
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- CN1974405A CN1974405A CN 200610147861 CN200610147861A CN1974405A CN 1974405 A CN1974405 A CN 1974405A CN 200610147861 CN200610147861 CN 200610147861 CN 200610147861 A CN200610147861 A CN 200610147861A CN 1974405 A CN1974405 A CN 1974405A
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Abstract
The present invention relates to preparation process of periodical nanometer titania line, is especially template process of preparing periodical nanometer titania line, and belongs to the field of nanometer material preparing technology. The present invention prepares periodical nanometer titania line by using alumina with periodical high ordered micropore array as template and through a sol-gel process. The present invention is superior to background technology in that the template process can obtain periodical nanometer titania line product with effectively controlled periodical distribution and size of nanometer titania lines, is simple, feasible, low in cost and pollution-free.
Description
Technical field
The present invention relates to a kind of preparation method of periodic nanometer titania line, definitely say, relate to method, belong to the technical field of nano material preparation with template preparation cycle titanium dioxide nano thread.
Background technology
The titanium dioxide of nanoscale has advantages such as suitable energy gap, advantages of high catalytic activity and nontoxic, good stability, at aspects such as photochemical catalysis, ultraviolet screener, opto-electronic conversion wide application prospect is arranged, extremely people pay close attention to, and have become an international research focus.
People are many to the research of nano TiO 2 powder at present, and quite few to the research of titanium dioxide nano thread, and are especially just fewer to the periodic nanometer titania line rapid detection.Because titanium oxide nanoparticles is tiny, the size distribution of particulate is also relatively disperseed, and with the titanium dioxide powder of general method (such as sol-gel method) preparation, is all to exist great restriction in its application facet or on to its research.Chinese patent CN1699636, proposing with metal inorganic salt and metal oxide is raw material, the utilization solvent-thermal method is prepared single crystal titanium dioxide nanowire.But required amount of medicament and quantity of solvent are more in this method, prepare more complicated, and constant temperature time is also longer in the preparation process, therefore operation inconvenience, and the nano wire chaotic of preparing.
Summary of the invention
For overcoming the shortcoming of prior art, improve the performance of titanium dioxide nano thread, the present invention proposes a kind of preparation method of periodic nanometer titania line.
For realizing above-mentioned purpose, the present invention by the following technical solutions.
Combine with sol-gel technique with periodicity template method: the aluminum oxide of the microwell array of, high-sequential periodic to contain is made template, makes product with sol-gel technique in the microwell array of its high-sequential, periodic nanometer titania line.The titanium dioxide nano thread that makes with this method is periodically, arranges regularly, and specific surface area is huge, the purity height of material, and density and characteristic are even, guarantee the product of the titanium dioxide nano thread that its arrangement that makes than background technology is unordered, have the performance of excellence more.In addition, every titanium dioxide nano thread is all corresponding with a micropore on the alumina formwork, can position single titanium dioxide nano thread.And all have pellumina to separate between nano wire and the nano wire, and can avoid the interference of average effect, help the characteristic of single nano-wire is carried out deep research.In addition, the diameter of the titanium dioxide nano thread of product is relevant closely with the microwell array of aluminium oxide nano-form with length, the aperture of the diameter of titanium dioxide nano thread and the micropore of aluminium oxide nano-form is suitable, the length of titanium dioxide nano thread is with different variation of hole depth of the micropore of aluminium oxide nano-form, therefore, adjust the aperture and the degree of depth of aluminium oxide nano-form, can prepare the titanium dioxide nano thread of different diameter and length.
Now describe technical scheme of the present invention in detail.
A kind of preparation method of periodic nanometer titania line is characterized in that, the concrete operations step:
It is aluminium flake more than 99.99% that the first step is got a purity, make matrix, with traditional method it being carried out cleaning surfaces handles: place organic solvent to carry out ultrasonic cleaning aluminium flake, clean after drying, place nitrogen atmosphere again, annealed 5 hours down at 500 ℃～620 ℃, be to carry out electrochemical etching in 1: 4 perchloric acid and the alcoholic acid mixing solutions in volume ratio then, polish temperature is 4～10 ℃, and polishing time is 20～40 seconds, cleans the aluminium flake surface with acid solution or alkaline solution at last;
It is the phosphoric acid solution of 0.1～0.5mol/L that second step will place concentration through the aluminium flake that the first step is handled, under 0 ℃～8 ℃, carry out the anodic oxidation first time, anodised voltage and current is elected 190 volts and 1mA～10mA respectively as, anodizing time is 3～8 hours, and negative electrode that anodic oxidation is used and anode are respectively platinized platinum and described aluminium flake;
The 3rd step will place chromic acid and phosphoric acid by any weight ratio blended mixing solutions through the aluminium flake that second step handled, and remove the oxide film on the aluminium flake;
The 4th step was neutralized trace with grating in the surface pressure of the aluminium flake of handling through the 3rd step: earlier grating is closely contacted with aluminium flake, grating is exerted pressure, surface at aluminium flake forms the wire impression, again grating is rotated 60 °, closely contact with aluminium flake, grating is exerted pressure, form netted impression on the surface of aluminium flake;
The 5th step was carried out the anodic oxidation second time to the aluminium flake of handling through the 4th step, and condition is identical with second step, formed the aluminium oxide nano-form of the microwell array that contains high-sequential at the netted impression place of aluminium flake;
The 6th step preparation A liquid and B liquid
At room temperature, preparation A liquid and B liquid, standby: the dehydrated alcohol of getting 10 volumes and 5 volumes is made the raw material of A liquid and B liquid respectively, the volume ratio that consists of tetrabutyl titanate, dehydrated alcohol and Glacial acetic acid of A liquid=1: 4: 1, the volume ratio that consists of dehydrated alcohol and deionized water of B liquid=10: 1;
The 7th step slowly was added dropwise to A liquid to B liquid, constantly stirred, and made it to become even colloidal sol, regulated pH value to 2～4 of colloidal sol again with hydrochloric acid;
The template that the 8th step obtained for the 5th step was boiled in the ebullient dehydrated alcohol 8～12 minutes, immersed in the colloidal sol of the 7th step preparation 15～55 minutes, air drying 20～28 hours, 530～590 ℃ of following thermal treatment 4 hours has made periodic nanometer titania line in the orderly micropore of porous aluminum template.
Fig. 1, Fig. 2 and Fig. 3 show the 4th respectively and go on foot grating, wire impression and the netted impression of addressing.Fig. 4 shows the aluminium oxide nano-form of the 5th microwell array that contains high-sequential addressed of step.
Technical scheme of the present invention is further characterized in that in the 3rd step, mixing solutions is mixed by the phosphoric acid of 6wt% and the chromic acid of 1.8wt%.
Technical scheme of the present invention is further characterized in that in the 4th step, the linear density of grating is every millimeter 1200 line, and the grating cycle is 0.833 micron.
Technical scheme of the present invention is further characterized in that in the 7th step, described stirring is a magnetic agitation, and stirring velocity is that per minute 50～160 changes.
Compare with background technology, the present invention has the following advantages:
1, preparation method of the present invention can control the distribution of titanium dioxide nano thread effectively, and it is had periodically, but also the size of may command titanium dioxide nano thread.
2, preparation method of the present invention is simple, and cost of manufacture is low, and is pollution-free.
Description of drawings
Fig. 1: the synoptic diagram of the grating of every millimeter 1200 line, the grating cycle of this grating is 0.833 micron.
Fig. 2: show with grating and suppress the wire impression that forms on the surface of aluminium flake after the aluminium flake for the first time.
Fig. 3: show with grating and suppress the netted impression that forms on the surface of aluminium flake after the aluminium flake for the second time.
Fig. 4: the synoptic diagram of the aluminum oxide porous structure of periodicity that finally forms after the aluminium flake oxidation on its surface.
Embodiment
Now describe technical scheme of the present invention in conjunction with the accompanying drawings and embodiments in detail.All embodiment all operate according to the operation steps of " summary of the invention " described method.Therefore, all embodiment is only enumerated the gordian technique data of each operation steps.
Embodiment one
In the first step, aluminium flake is of a size of 20mm*20mm, anneals 5 hours down for 500 ℃, and polish temperature is 4 ℃, and polishing time is 40 seconds; In second step, will place concentration through the aluminium flake that the first step is handled is the phosphoric acid solution of 0.1mol/L, under 0 ℃, carries out the anodic oxidation first time, and anodised electric current is 10mA, and anodizing time is 3 hours; In the 4th step, grating is the reflective gratings that is respectively every millimeter 1200 line and 0.833 micron in raster density and grating cycle; In the 6th step, the volume ratio that consists of tetrabutyl titanate 5mL, dehydrated alcohol 20mL and Glacial acetic acid 5mL of A liquid=1: 4: 1, the volume ratio that consists of dehydrated alcohol 10mL and deionized water 1mL of B liquid=10: 1; In the 7th step, the pH value to 2 of regulating colloidal sol; In the 8th step, the 5th template that obtain of step was boiled in the ebullient dehydrated alcohol 8 minutes, immersed in the colloidal sol that the 7th step prepared 15 minutes, air drying 20 hours, 530 ℃ of following thermal treatment 4 hours.
Embodiment two
In the first step, aluminium flake is of a size of 20mm*20mm, anneals 5 hours down for 560 ℃, and polish temperature is 7 ℃, and polishing time is 30 seconds; In second step, will place concentration through the aluminium flake that the first step is handled is the phosphoric acid solution of 0.3mol/L, under 4 ℃, carries out the anodic oxidation first time, and anodised electric current is 5.5mA, and anodizing time is 5.5 hours; In the 4th step, grating is the reflective gratings that is respectively every millimeter 1200 line and 0.833 micron in raster density and grating cycle; In the 6th step, the volume ratio that consists of tetrabutyl titanate 5mL, dehydrated alcohol 20mL and Glacial acetic acid 5mL of A liquid=1: 4: 1, the volume ratio that consists of dehydrated alcohol 10mL and deionized water 1mL of B liquid=10: 1; In the 7th step, the pH value to 3 of regulating colloidal sol; In the 8th step, the 5th template that obtain of step was boiled in the ebullient dehydrated alcohol 10 minutes, immersed in the colloidal sol that the 7th step prepared 30 minutes, air drying 24 hours, 560 ℃ of following thermal treatment 4 hours.
Embodiment three
In the first step, aluminium flake is of a size of 20mm*20mm, anneals 5 hours down for 620 ℃, and polish temperature is 10 ℃, and polishing time is 20 seconds; In second step, will place concentration through the aluminium flake that the first step is handled is the phosphoric acid solution of 0.5mol/L, under 8 ℃, carries out the anodic oxidation first time, and anodised electric current is 1mA, and anodizing time is 8 hours; In the 4th step, grating is the reflective gratings that is respectively every millimeter 1200 line and 0.833 micron in raster density and grating cycle; In the 6th step, the volume ratio that consists of tetrabutyl titanate 5mL, dehydrated alcohol 20mL and Glacial acetic acid 5mL of A liquid=1: 4: 1, the volume ratio that consists of dehydrated alcohol 10mL and deionized water 1mL of B liquid=10: 1; In the 7th step, the pH value to 4 of regulating colloidal sol; In the 8th step, the 5th template that obtain of step was boiled in the ebullient dehydrated alcohol 12 minutes, immersed in the colloidal sol that the 7th step prepared 55 minutes, air drying 28 hours, 590 ℃ of following thermal treatment 4 hours.
Claims (5)
1, a kind of preparation method of periodic nanometer titania line is characterized in that, the concrete operations step:
It is aluminium flake more than 99.99% that the first step is got a purity, make matrix, with traditional method it being carried out cleaning surfaces handles: place organic solvent to carry out ultrasonic cleaning aluminium flake, clean after drying, place nitrogen atmosphere again, annealed 5 hours down at 500 ℃～620 ℃, be to carry out electrochemical etching in 1: 4 perchloric acid and the alcoholic acid mixing solutions in volume ratio then, polish temperature is 4～10 ℃, and polishing time is 20～40 seconds, cleans the aluminium flake surface with acid solution or alkaline solution at last;
It is the phosphoric acid solution of 0.1～0.5mol/L that second step will place concentration through the aluminium flake that the first step is handled, under 0 ℃～8 ℃, carry out the anodic oxidation first time, anodised voltage and current is elected 190 volts and 1mA～10mA respectively as, anodizing time is 3～8 hours, and negative electrode that anodic oxidation is used and anode are respectively platinized platinum and described aluminium flake;
The 3rd step will place chromic acid and phosphoric acid by any weight ratio blended mixing solutions through the aluminium flake that second step handled, and remove the oxide film on the aluminium flake;
The 4th step was neutralized trace with grating in the surface pressure of the aluminium flake of handling through the 3rd step: earlier grating is closely contacted with aluminium flake, grating is exerted pressure, surface at aluminium flake forms the wire impression, again grating is rotated 60 °, closely contact with aluminium flake, grating is exerted pressure, form netted impression on the surface of aluminium flake;
The 5th step was carried out the anodic oxidation second time to the aluminium flake of handling through the 4th step, and condition is identical with second step, formed the aluminium oxide nano-form of the microwell array that contains high-sequential at the netted impression place of aluminium flake;
The 6th step preparation A liquid and B liquid
At room temperature, preparation A liquid and B liquid, standby: the dehydrated alcohol of getting 10 volumes and 5 volumes is made the raw material of A liquid and B liquid respectively, the volume ratio that consists of tetrabutyl titanate, dehydrated alcohol and Glacial acetic acid of A liquid=1: 4: 1, the volume ratio that consists of dehydrated alcohol and deionized water of B liquid=10: 1;
The 7th step slowly was added dropwise to A liquid to B liquid, constantly stirred, and made it to become even colloidal sol, regulated pH value to 2～4 of colloidal sol again with hydrochloric acid;
The template that the 8th step obtained for the 5th step was boiled in the ebullient dehydrated alcohol 8～12 minutes, immersed in the colloidal sol of the 7th step preparation 15～55 minutes, air drying 20～28 hours, 530～590 ℃ of following thermal treatment 4 hours has made periodic nanometer titania line in the orderly micropore of porous aluminum template.
2, the preparation method of periodic nanometer titania line according to claim 1 is characterized in that, in the 3rd step, mixing solutions is mixed by the phosphoric acid of 6wt% and the chromic acid of 1.8wt%.
3, the preparation method of periodic nanometer titania line according to claim 1 is characterized in that, in the 4th step, the linear density of grating is every millimeter 1200 line, and the grating cycle is 0.833 micron.
4, the preparation method of periodic nanometer titania line according to claim 1 is characterized in that, in the 7th step, described stirring is a magnetic agitation, and stirring velocity is that per minute 50～160 changes.
5, the preparation method of periodic nanometer titania line according to claim 1, it is characterized in that, in the 3rd step, mixing solutions is mixed by the phosphoric acid of 6wt% and the chromic acid of 1.8wt%, and in the 4th step, the linear density of grating is every millimeter 1200 line, the grating cycle is 0.833 micron, in the 7th step, described stirring is a magnetic agitation, and stirring velocity is that per minute 50～160 changes.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101319393B (en) * | 2008-06-18 | 2010-09-22 | 哈尔滨工业大学 | Preparation method of strontium bismuth tantalite nanometer line |
| CN101319405B (en) * | 2007-06-08 | 2011-05-18 | 中国科学院苏州纳米技术与纳米仿生研究所 | Production method of TiO2 nanotube and/or TiO2 nano-whisker |
| CN105036188A (en) * | 2015-07-07 | 2015-11-11 | 上海理工大学 | Titanium dioxide nanowire and preparation method thereof |
| CN109326790A (en) * | 2018-08-30 | 2019-02-12 | 中国石油天然气股份有限公司 | A kind of 1-dimention nano threadiness sodium titanate and its preparation method and application |
-
2006
- 2006-12-25 CN CNB2006101478618A patent/CN100513319C/en not_active Expired - Fee Related
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101319405B (en) * | 2007-06-08 | 2011-05-18 | 中国科学院苏州纳米技术与纳米仿生研究所 | Production method of TiO2 nanotube and/or TiO2 nano-whisker |
| CN101319393B (en) * | 2008-06-18 | 2010-09-22 | 哈尔滨工业大学 | Preparation method of strontium bismuth tantalite nanometer line |
| CN105036188A (en) * | 2015-07-07 | 2015-11-11 | 上海理工大学 | Titanium dioxide nanowire and preparation method thereof |
| CN105036188B (en) * | 2015-07-07 | 2017-03-01 | 上海理工大学 | A kind of titanium dioxide nano thread and preparation method thereof |
| CN109326790A (en) * | 2018-08-30 | 2019-02-12 | 中国石油天然气股份有限公司 | A kind of 1-dimention nano threadiness sodium titanate and its preparation method and application |
| CN109326790B (en) * | 2018-08-30 | 2021-08-03 | 中国石油天然气股份有限公司 | One-dimensional nano linear sodium titanate and preparation method and application thereof |
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| CN100513319C (en) | 2009-07-15 |
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