CN101054711A - Method of preparing titanium dioxide thin film by oxidizing metallic titanium using alternating current - Google Patents
Method of preparing titanium dioxide thin film by oxidizing metallic titanium using alternating current Download PDFInfo
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- CN101054711A CN101054711A CN 200710040493 CN200710040493A CN101054711A CN 101054711 A CN101054711 A CN 101054711A CN 200710040493 CN200710040493 CN 200710040493 CN 200710040493 A CN200710040493 A CN 200710040493A CN 101054711 A CN101054711 A CN 101054711A
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Abstract
The invention belongs to the technical field of TiO2 membrane preparation. In particular, the invention relates to a method for TiO2 membrane preparation by metal Ti oxidation with AC. The method uses AC electrolysis device, metal Ti sheet as the working electrode and black lead as the counter electrode, adjusts the current passing through the metal Ti sheet by adjusting the input voltage and obtains Ti-based TiO2 membrane via oxidizing the metal Ti sheep directly. The oxidation temperature is 0-100 degree, the voltage is 10-50V and the time lasts for 1-30min. The invention is characterized in simple device and process, convenient control and good photoelectric performance of the prepared TiO2 membrane.
Description
Technical field
The invention belongs to the titanium deoxid film preparing technical field, be specifically related to a kind of novel method for preparing the nanometer titania film by alternating-current direct oxidation metal titanium sheet.
Background technology
Found semi-conductor titanium dioxide since splitting water into hydrogen and oxygen under the UV-irradiation from 1972, titanium dioxide has been subjected in the material field paying attention to widely.TiO
2Can be used for many aspects such as photocatalysis to degrade organic matter, sterilization and disinfection, sewage disposal, purifying air, photochemical catalyzing.Titanium deoxid film preparation technology's research is nano-TiO
2Basis and prerequisite that photochemical catalysis and opto-electronic conversion etc. are used.At present, nano-TiO
2Preparation method's research become a very active problem of photochemical catalysis novel material exploitation, the TiO that has reported
2Method for manufacturing thin film is a lot, for example reaction magnetocontrol sputtering, sol-gel process, chemical gaseous phase depositing process etc., and these methods respectively have its relative merits.As with physics methods such as direct current reaction magnetron sputterings at glass surface depositing Ti O
2Film, the self-cleaning glass that obtains have the good transparency, stronger photocatalysis performance and photic Superhydrophilic, film evenly, controllable thickness, but must vacuum system, the equipment price costliness, sputter rate also is one of bottleneck of its widespread use of restriction in addition; Use sol-gel method and prepare TiO
2Film has the purity height, reaction conditions is easy to advantages such as control, but has certain degree of difficulty in preparation large area film fashion.Also can on the substrate of conduction, prepare TiO by electrochemical deposition technique
2Film.Titanium base/titanium dioxide membrane electrode provided has a good application prospect and obtains paying attention in many aspects such as electrochemical industry, photochemical catalysis.Heated oxide metal titanium sheet or application flame heating oxidizing metallic titanium using sheet all can obtain TiO in muffle furnace
2Film.In certain solution, apply volts DS the metal titanium sheet anodic oxidation also can be formed nanostructure TiO on its surface
2Film is used to prepare the nanostructure TiO with photoelectric activity and use the oxidizing metallic titanium using alternating current sheet
2The research of film does not appear in the newspapers.
Summary of the invention
The objective of the invention is to propose a kind of technology simple, control nano-titanium dioxide film preparation method easily.
The present invention is a kind of method for preparing nano-titanium dioxide film with the oxidizing metallic titanium using alternating current sheet, use the alternating current electrolysis device, this device is provided with AC power source voltage regulator, electrolyzer, stirrer, reometer and voltmeter, with metal titanium sheet as working electrode, with graphite is counter electrode, and electrolytic solution is by the NH of 0.5-1M
4SO
4NH with this composition weight 0.1-1wt%
4F forms.Preparation facilities is seen synoptic diagram 1.Regulate the input voltage of voltate regulator, thereby flow through the electric current of metal titanium sheet with adjusting, the direct oxidation metal titanium sheet obtains the titanium-based titanium dioxide film; Temperature during oxidation is 0～100 ℃, and control voltage is 10-50V, and be 1～30min conduction time.In the process of energising, the oxidized formation of the Ti TiO on surface
2Film, membrane structure are as shown in Figure 2.
Experiment shows that the nano-titanium dioxide film that is prepared by the present invention is anatase octahedrite and rutile mixing crystal formation, presents the vesicular nanostructure, has the feature and the excellent photoelectric performance of typical n N-type semiconductorN.
1. under white light, with the TiO of the present invention's preparation
2Film shows tangible anode photoelectric current, and density of photocurrent is about 0.22～0.24mA.cm during 0V
-2,, the nano-TiO by this novel method preparation is described as Fig. 3 and shown in Figure 6
2Film has the feature of typical n N-type semiconductorN, can be applied in solar energy photoelectric conversion and photochemical catalyzing.
2. the XRD test shows of film is with the TiO of the present invention's preparation
2Membrane structure is anatase octahedrite and rutile mixing crystal formation, as shown in Figure 4.
3. the SEM test shows of film is with the TiO of the present invention's preparation
2Membrane structure is the vesicular double-layer structure, as Fig. 5 and shown in Figure 7.Titanium metal is through after the anodic oxidation, and the surface presents significantly two-layer, and wherein top one deck is made up of about 1 micron aggregate, and the second layer is to be made of cavernous sponge figure oxide film.And work as voltage and oxidization time not simultaneously, surface topography also presents different phenomenons.Aggregate is formed by many very little particle aggregations together, and surface arrangement is irregular, and particle size distribution is inhomogeneous.Oxide film shows cell texture, and pore size distribution is inhomogeneous, and the aperture and communicates between the Kong Yukong below 100nm.
The inventive method uses equipment and technology simply to control conveniently, prepares TiO
2Film photoelectric is functional.
Description of drawings
Fig. 1 AC Anodizing titanium sheet prepares TiO
2Film experimental installation synoptic diagram.
Fig. 2 TiO
2The structural representation of film.
Fig. 3 AC Anodizing titanium sheet prepares TiO
2The photoelectric current of film is measured, a, and photoelectric current b, (voltage of alternating current 50V, oxidization time are 3min to dark current, 450 ℃ of thermal treatment 1 hour, xenon source, white light 250mW/cm
2).
The TiO of Fig. 4 oxidizing metallic titanium using alternating current sheet preparation
2(voltage of alternating current 20V, solution are 0.5M (NH to the XRD spectrum of film
4)
2SO
4And 0.5wt%NH
4F solution, oxidization time 10min was through 450 ℃ of thermal treatments 2 hours.
The TiO of Fig. 5 oxidizing metallic titanium using alternating current sheet preparation
2The SEM spectrum of film (alternating-current 50V, oxidization time 3min, not thermal treatment, solution is 0.5M (NH
4)
2SO
4+ 0.5wt.%NH
4F).
The TiO of Fig. 6 AC Anodizing titanium sheet preparation
2The photoelectric current of film is measured, a, photoelectric current b, dark current (voltage of alternating current 20V, oxidization time 3min, 450 ℃ of thermal treatment 1 hour, xenon source, white light 250mW/cm
2)
The TiO of Fig. 7 oxidizing metallic titanium using alternating current sheet preparation
2SEM spectrum (alternating-current 40V, oxidization time 3min, not thermal treatment, the 0.5M (NH of film
4)
2SO
4+ 0.5wt.%NH
4F).
Number in the figure 1 is the metal Ti electrode, and 2 is counter electrode (graphite), and 3 is electrolyzer, and 4 is magnetic stir bar, and 5 is voltate regulator, and 6 is voltmeter, and 7 is reometer, and 8 is TiO
2Film, 9 is the titanium substrate.
Embodiment
Embodiment 1: (thickness is 0.25mm to the metal titanium sheet after will cleaning, area 1cm
2) be fixed in the electrolyzer 3 as working electrode 1, counter electrode 2 is a graphite, working electrode 1 and counter electrode 2 are connected the output terminal of voltate regulator 5 by lead, two interelectrode distances remain on 2cm, the input voltage of regulating voltate regulator 5 is 50V, oxidization time is 3min, the oxidized TiO that obtains of metal titanium sheet
2Film.Through 450 ℃ of thermal treatments after 2 hours, the TiO that obtains
2The density of photocurrent when 0V of film is 0.24mA.cm
-2, as shown in Figure 3.
Embodiment 2: (thickness is 0.25mm to the metal titanium sheet after will cleaning, area 1cm
2) be fixed in the electrolyzer 3 as working electrode 1, counter electrode 2 is a graphite, working electrode 1 and counter electrode 2 are connected the output terminal of voltate regulator 5 by lead, two interelectrode distances remain on 2cm, the input voltage of regulating voltate regulator is 20V, oxidization time is 10min, the oxidized TiO that obtains of metal titanium sheet
2Film.The TiO that obtain behind the 10min conduction time
2Film is through 450 ℃ of thermal treatments after 2 hours, the TiO that obtains
2The XRD spectrum of film is for shown in Figure 4.As can be seen from Figure 4, with the TiO of this prepared
2Film is anatase octahedrite and rutile mixing crystal formation.
Embodiment 3: (thickness is 0.25mm to the metal titanium sheet after will cleaning, area 1cm
2) be fixed in the electrolyzer 3 as working electrode 1, counter electrode 2 is a graphite, working electrode 1 and counter electrode 2 are connected the output terminal of voltate regulator 5 by lead, two interelectrode distances remain on 2cm, the input voltage of regulating voltate regulator is 50V, oxidization time is 3min, the oxidized TiO that obtains of metal titanium sheet
2Film.The TiO that obtain behind the 30min conduction time
2The SEM spectrum of film is for shown in Figure 5.As can be seen from Figure 5, with the TiO of this prepared
2Film is the vesicular bilayer structure.
Embodiment 4: (thickness is 0.25mm to the metal titanium sheet after will cleaning, area 1cm
2) be fixed in the electrolyzer 3 as working electrode 1, counter electrode 2 is a graphite, working electrode 1 and counter electrode 2 are connected the output terminal of voltate regulator 5 by lead, two interelectrode distances remain on 2cm, the input voltage of regulating voltate regulator is 20V, oxidization time is 3min, the oxidized TiO that obtains of metal titanium sheet
2Film.Through 450 ℃ of thermal treatments after 2 hours, the TiO that obtains
2The density of photocurrent when 0V of film is 0.22mA.cm
-2, a little less than the TiO that obtains in the 50V oxidation
2The photoelectric current of film sample.As shown in Figure 6.
Embodiment 5: (thickness is 0.25mm to the metal titanium sheet after will cleaning, area 1cm
2) be fixed in the electrolyzer 3 as working electrode 1, counter electrode 2 is a graphite, working electrode 1 and counter electrode 2 are connected the output terminal of voltate regulator 5 by lead, two interelectrode distances remain on 2cm, the input voltage of regulating voltate regulator is 40V, oxidization time is 3min, the oxidized TiO that obtains of metal titanium sheet
2Film.The TiO that obtain behind the 30min conduction time
2The SEM spectrum of film is for shown in Figure 7.As can be seen from Figure 7, with the TiO of this prepared
2Film is the vesicular bilayer structure, the TiO that obtains with respect to oxidation under 50V
2Film sample, hole reduces.
Claims (1)
1, a kind of method of preparing titanium dioxide thin film by oxidizing metallic titanium using alternating current, it is characterized in that concrete steps are as follows: use the alternating current electrolysis device, this device is provided with AC power source voltage regulator, electrolyzer, stirrer, reometer and voltmeter, with metal titanium sheet as working electrode, with graphite is counter electrode, and electrolytic solution is by the NH of 0.5-1M
4SO
4NH with this composition weight 0.1-1wt%
4F forms; Regulate the input voltage of voltate regulator, thereby flow through the electric current of metal titanium sheet with adjusting, the direct oxidation metal titanium sheet obtains the titanium-based titanium dioxide film; Temperature during oxidation is 0～100 ℃, and control voltage is 10-50V, and be 1～30min conduction time.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200710040493 CN101054711A (en) | 2007-05-10 | 2007-05-10 | Method of preparing titanium dioxide thin film by oxidizing metallic titanium using alternating current |
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|---|---|
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101733084B (en) * | 2009-12-22 | 2011-12-21 | 哈尔滨工业大学 | Preparation device of large-area titanium dioxide thin film catalyst and preparation method thereof |
| CN103097588A (en) * | 2010-07-19 | 2013-05-08 | 莱顿大学 | Process to prepare metal nanoparticles or metal oxide nanoparticles |
| CN103730637A (en) * | 2014-01-10 | 2014-04-16 | 纪效波 | Method for preparing negative electrode material lithium titanate of lithium ion battery through alternating voltage method |
| TWI466747B (en) * | 2010-11-18 | 2015-01-01 | Univ Nat Taiwan | Production method of dyed white titanium contained metal |
| CN109750339A (en) * | 2019-03-25 | 2019-05-14 | 四川农业大学 | With absorption visible light and near-infrared mixing appearance structure optoelectronic pole and preparation method |
-
2007
- 2007-05-10 CN CN 200710040493 patent/CN101054711A/en active Pending
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101733084B (en) * | 2009-12-22 | 2011-12-21 | 哈尔滨工业大学 | Preparation device of large-area titanium dioxide thin film catalyst and preparation method thereof |
| CN103097588A (en) * | 2010-07-19 | 2013-05-08 | 莱顿大学 | Process to prepare metal nanoparticles or metal oxide nanoparticles |
| CN103097588B (en) * | 2010-07-19 | 2016-10-26 | 莱顿大学 | A kind of method preparing metal nanoparticle or metal oxide nanoparticles |
| US9695521B2 (en) | 2010-07-19 | 2017-07-04 | Universiteit Leiden | Process to prepare metal nanoparticles or metal oxide nanoparticles |
| TWI466747B (en) * | 2010-11-18 | 2015-01-01 | Univ Nat Taiwan | Production method of dyed white titanium contained metal |
| CN103730637A (en) * | 2014-01-10 | 2014-04-16 | 纪效波 | Method for preparing negative electrode material lithium titanate of lithium ion battery through alternating voltage method |
| CN103730637B (en) * | 2014-01-10 | 2016-04-20 | 纪效波 | A kind of alternating voltage method prepares the method for lithium ionic cell cathode material lithium titanate |
| CN109750339A (en) * | 2019-03-25 | 2019-05-14 | 四川农业大学 | With absorption visible light and near-infrared mixing appearance structure optoelectronic pole and preparation method |
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