CN102534727A - Titanium dioxide nanocomposite and one-step preparation method by utilizing anodic oxidation device - Google Patents
Titanium dioxide nanocomposite and one-step preparation method by utilizing anodic oxidation device Download PDFInfo
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- CN102534727A CN102534727A CN2012100108036A CN201210010803A CN102534727A CN 102534727 A CN102534727 A CN 102534727A CN 2012100108036 A CN2012100108036 A CN 2012100108036A CN 201210010803 A CN201210010803 A CN 201210010803A CN 102534727 A CN102534727 A CN 102534727A
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Abstract
The invention discloses a titanium dioxide nanocomposite and a one-step preparation method by utilizing an anodic oxidation device; the preparation method comprises the steps of: polishing a pure titanium sheet to be smooth, cleaning ultrasonically and drying, fixing the pure titanium sheet to an anode by the anodic oxidation device, fixing a platinum gauze electrode to a cathode, and placing the pure titanium sheet and the platinum gauze electrode into electrolyte to perform an electrochemical reaction, wherein the electrolyte is an ethylene glycol/water mixing solution of ammonium fluoride, the concentration of NH4F in the solution is 0.1wt%-0.5wt%, the volume ratio of water is 1vol%-5vol%, the temperature of the solution is kept to be 20 DEG C-60 DEG C,the reaction time is 16 hours-48 hours, and the anodic oxidation voltage is 50V-70V. In the invention, the preparation process with low cost and simple preparation process is provided, a composite structure material of a nanotube and a nanowire in a microstructure can be provided, and good photoelectric efficiency is achieved.
Description
Technical field
The present invention relates to a kind of nano material and preparation method thereof, more particularly, relate to electrode materials as the photocatalysis field solar cell and preparation method thereof.
Background technology
At present, because energy shortage is serious day by day, the sun power that people begin to seek green high-efficient substitutes traditional energy.Chinese scholars begins one's study and has the photocatalyst of big reference area at present, thereby effectively improves the efficient of solar cell.Titania nanotube has low, the big specific surface area of preparation cost, the surface topography of rule, advantageous property such as light stability and unreactiveness preferably, becomes one of most popular photocatalyst.At present be further to improve TiO
2The photocatalysis efficiency of nanotube; Investigators adopt preparations such as anonizing, hydrothermal synthesis method to have the self-assembled nanometer pipe of different lengths, different tube diameters; Yet the nanotube length for preparing all is lower than 30 μ m, and can not to satisfy fully with the titania nanotube be the requirement of the solar cell of electrode materials to length to the nanotube of length like this.
Summary of the invention
The objective of the invention is to overcome the deficiency of prior art, provide that a kind of cost is low, the simple preparation technology of preparation process, a kind of sandwich of on microtexture, realizing nanotube and nano wire can be provided.
The object of the invention is achieved through following technical proposals:
Utilize the anodic oxidation device single stage method to prepare self-assembled nanometer pipe and nano wire compound nanostructure; After pure titanium sheet polished smooth, ultrasonic more clean after drying then was fixed in anode with anodic oxidation device with pure titanium sheet; The platinized platinum electrode is fixed in negative electrode; Both place electrolytic solution to carry out electrochemical reaction, and wherein electrolytic solution is the glycol/water mixing solutions of Neutral ammonium fluoride, NH in the solution
4The concentration of F is 0.1wt%-0.5wt%, and the percent by volume of water is 1vol%-5vol%, and solution temperature remains on 20 ℃-60 ℃, and anodizing time is 16h-48h, and anodic oxidation voltage is 50V-70V.
NH in the said electrolytic solution
4The concentration of F is preferably 0.2wt%-0.5wt%.
The percent by volume of water is preferably 3vol%-5vol% in the said electrolytic solution.
Said solution temperature remains on 30 ℃-50 ℃, and anodizing time is 20h-40h, and anodic oxidation voltage is 55V-68V.
Technical scheme of the present invention is more than the 100 μ m in the nanotube length for preparing with anonizing on the pure titanium sheet; Nanotube upper strength deficiency is caved in the back by the unidirectional corrosion of continuation; Tubular structure is continued to extend in the nanotube bottom; Therefore finally obtain the NEW TYPE OF COMPOSITE structure that nanotube surface covers nano wire (shown in accompanying drawing 1-5, S4800; Hitachi, Japan), all greater than 100 μ m, tube wall is smooth for the titania nanotube pipe range for preparing, and the pipe upper surface has equally distributed titanium dioxide nano thread structure (shown in accompanying drawing 6).The titanic oxide material that will have this composite nanostructure carries out the photoelectric current experiment as the light anode, selects the 0.1mol/L aqueous sodium persulfate solution for use, and (power is 130mW/cm to the xenon lamp of CHF-XM-500w
2) as light source, current density can reach 0.6mA/cm
2, explain that the titanium oxide of composite nanostructure has excellent photoelectric performance (shown in accompanying drawing 7).
Description of drawings
Fig. 1 TiO
2(ESEM is S4800 to the surperficial SEM pattern of nanotube and nano wire compound novel nano structure; Hitachi, Japan) (electrolytic solution is formed: NH
4F concentration is 0.3wt%, and the volume ratio of water is 2vol%, anodizing time 20h, 20 ℃ of anodic oxidation temperature)
Fig. 2 TiO
2(ESEM is S4800 to the surperficial SEM pattern of nanotube and nano wire compound novel nano structure; Hitachi, Japan) (electrolytic solution is formed: NH
4F concentration is 0.3wt%, and the volume ratio of water is 2vol%, anodizing time 20h, 20 ℃ of anodic oxidation temperature)
Fig. 3 TiO
2(ESEM is S4800 to the whole SEM pattern in the side of nanotube and nano wire compound novel nano structure; Hitachi, Japan) (electrolytic solution is formed: NH
4F concentration is 0.3wt%, and the volume ratio of water is 2vol%, anodizing time 20h, 20 ℃ of anodic oxidation temperature)
Fig. 4 TiO
2(ESEM is S4800 to the lateral parts SEM pattern of nanotube and nano wire compound novel nano structure; Hitachi, Japan) (electrolytic solution is formed: NH
4F concentration is 0.3wt%, and the volume ratio of water is 2vol%, anodizing time 20h, 20 ℃ of anodic oxidation temperature)
Fig. 5 TiO
2(ESEM is S4800 to the SEM pattern at the bottom of the pipe of nanotube and nano wire compound novel nano structure; Hitachi, Japan) (electrolytic solution is formed: NH
4F concentration is 0.3wt%, and the volume ratio of water is 2vol%, anodizing time 20h, 20 ℃ of anodic oxidation temperature)
The XRD spectra of the nanometer titania of Fig. 6 self-assembly after 450 ℃ of annealing (RIGAKU/DMAX2500, Japan)
The nano composite material that Fig. 7 utilizes the present invention to prepare is carried out photoelectric current result of experiment figure
Embodiment
Further specify technical scheme of the present invention below in conjunction with embodiment, wherein pure titanium sheet is fixed in anode, the platinized platinum electrode is fixed in negative electrode, and the electrochemical workstation of employing is Gamry Reference 600.
Embodiment 1
Anonizing is to utilize the constant voltage power supply instrument, adopts two electrode systems (anode is pure titanium sheet, and negative electrode is a platinized platinum) at NH
4The method of prepared in reaction nano material in the F-glycol/water mixing solutions.
The processing parameter that adopts during anodic oxidation constitutes is:
Anodic oxidation voltage: 60V
Anodic oxidation temperature (solution temperature): 20 ℃
Anodizing time: 20h
Concentration of electrolyte: NH
4F concentration is 0.3wt%, and the percent by volume of water is 2vol%
Its step of the preparation method of above-mentioned said novel nano-material is following:
(1) use 240#, 400#, 600#, 800#, 1500#, 2000#, 3000# sand papering to smooth successively pure titanium sheet, the back cleans up the ultrasonic 5min after drying of absolute ethyl alcohol with deionized water.
(2) pure titanium sheet is packed in the anodic oxidation device, feed constant voltage 60V, the time is 20h, prepares self-assembly TiO
2Nanostructure.
(3) sample is taken out, with absolute ethyl alcohol ultrasonic cleaning after drying.
Embodiment 2
Anonizing is to utilize the constant voltage power supply instrument, adopts two electrode systems (anode is pure titanium sheet, and negative electrode is a platinized platinum) at NH
4The method of prepared in reaction nano material in the F-glycol/water mixing solutions.
The processing parameter that adopts during anodic oxidation constitutes is:
Anodic oxidation voltage: 50V
Anodic oxidation temperature (solution temperature): 30 ℃
Anodizing time: 16h
Concentration of electrolyte: NH
4F concentration is 0.2wt%, and the percent by volume of water is 5vol%
Its step of the preparation method of above-mentioned said novel nano-material is following:
(1) use 240#, 400#, 600#, 800#, 1500#, 2000#, 3000# sand papering to smooth successively pure titanium sheet, the back cleans up the ultrasonic 5min after drying of absolute ethyl alcohol with deionized water.
(2) pure titanium sheet is packed in the anodic oxidation device, feed constant voltage 50V, the time is 16h, prepares self-assembly TiO
2Nanostructure.
(3) sample is taken out, with absolute ethyl alcohol ultrasonic cleaning after drying.
Embodiment 3
Anonizing is to utilize the constant voltage power supply instrument, adopts two electrode systems (anode is pure titanium sheet, and negative electrode is a platinized platinum) at NH
4The method of prepared in reaction nano material in the F-glycol/water mixing solutions.
The processing parameter that adopts during anodic oxidation constitutes is:
Anodic oxidation voltage: 70V
Anodic oxidation temperature (solution temperature): 60 ℃
Anodizing time: 48h
Concentration of electrolyte: NH
4F concentration is 0.1wt%, and the percent by volume of water is 3vol%
Its step of the preparation method of above-mentioned said novel nano-material is following:
(1) use 240#, 400#, 600#, 800#, 1500#, 2000#, 3000# sand papering to smooth successively pure titanium sheet, the back cleans up the ultrasonic 5min after drying of absolute ethyl alcohol with deionized water.
(2) pure titanium sheet is packed in the anodic oxidation device, feed constant voltage 70V, the time is 48h, prepares self-assembly TiO
2Nanostructure.
(3) sample is taken out, with absolute ethyl alcohol ultrasonic cleaning after drying.
Embodiment 4
Anonizing is to utilize the constant voltage power supply instrument, adopts two electrode systems (anode is pure titanium sheet, and negative electrode is a platinized platinum) at NH
4The method of prepared in reaction nano material in the F-glycol/water mixing solutions.
The processing parameter that adopts during anodic oxidation constitutes is:
Anodic oxidation voltage: 55V
Anodic oxidation temperature (solution temperature): 50 ℃
Anodizing time: 40h
Concentration of electrolyte: NH
4F concentration is 0.5wt%, and the percent by volume of water is 1vol%
Its step of the preparation method of above-mentioned said novel nano-material is following:
(1) use 240#, 400#, 600#, 800#, 1500#, 2000#, 3000# sand papering to smooth successively pure titanium sheet, the back cleans up the ultrasonic 5min after drying of absolute ethyl alcohol with deionized water.
(2) pure titanium sheet is packed in the anodic oxidation device, feed constant voltage 55V, the time is 40h, prepares self-assembly TiO
2Nanostructure.
(3) sample is taken out, with absolute ethyl alcohol ultrasonic cleaning after drying.
Embodiment 5
Anonizing is to utilize the constant voltage power supply instrument, adopts two electrode systems (anode is pure titanium sheet, and negative electrode is a platinized platinum) at NH
4The method of prepared in reaction nano material in the F-glycol/water mixing solutions.
The processing parameter that adopts during anodic oxidation constitutes is:
Anodic oxidation voltage: 68V
Anodic oxidation temperature (solution temperature): 35 ℃
Anodizing time: 30h
Concentration of electrolyte: NH
4F concentration is 0.4wt%, and the percent by volume of water is 4vol%
Its step of the preparation method of above-mentioned said novel nano-material is following:
(1) use 240#, 400#, 600#, 800#, 1500#, 2000#, 3000# sand papering to smooth successively pure titanium sheet, the back cleans up the ultrasonic 5min after drying of absolute ethyl alcohol with deionized water.
(2) pure titanium sheet is packed in the anodic oxidation device, feed constant voltage 68V, the time is 30h, prepares self-assembly TiO
2Nanostructure.
(3) sample is taken out, with absolute ethyl alcohol ultrasonic cleaning after drying.
More than the present invention has been done exemplary description; Should be noted that; Under the situation that does not break away from core of the present invention, the replacement that is equal to that any simple distortion, modification or other those skilled in the art can not spend creative work all falls into protection scope of the present invention.
Claims (6)
1. a titanic oxide nano compound material has titania nanotube and nano thread structure, it is characterized in that; Prepare according to following step: after pure titanium sheet was polished smooth, ultrasonic more clean after drying then was fixed in anode with anodic oxidation device with pure titanium sheet; The platinized platinum electrode is fixed in negative electrode; Both place electrolytic solution to carry out electrochemical reaction, and wherein electrolytic solution is the glycol/water mixing solutions of Neutral ammonium fluoride, NH in the solution
4The concentration of F is 0.1wt%-0.5wt%, and the percent by volume of water is 1vol%-5vol%, and solution temperature remains on 20 ℃-60 ℃, and anodizing time is 16h-48h, and anodic oxidation voltage is 50V-70V.
2. a kind of titanic oxide nano compound material according to claim 1 is characterized in that, NH in the said electrolytic solution
4The concentration of F is preferably 0.2wt%-0.5wt%, and the percent by volume of water is preferably 3vol%-5vol%.
3. a kind of titanic oxide nano compound material according to claim 1 is characterized in that, said solution temperature remains on 30 ℃-50 ℃, and anodizing time is 20h-40h, and anodic oxidation voltage is 55V-68V.
4. utilize the anodic oxidation device single stage method to prepare the method for titanic oxide nano compound material, it is characterized in that, carry out: after pure titanium sheet is polished smooth according to following step; Ultrasonic more clean after drying; Then with anodic oxidation device pure titanium sheet is fixed in anode, the platinized platinum electrode is fixed in negative electrode, and both place electrolytic solution to carry out electrochemical reaction; Wherein electrolytic solution is the glycol/water mixing solutions of Neutral ammonium fluoride, NH in the solution
4The concentration of F is 0.1wt%-0.5wt%, and the percent by volume of water is 1vol%-5vol%, and solution temperature remains on 20 ℃-60 ℃, and anodizing time is 16h-48h, and anodic oxidation voltage is 50V-70V.
5. the method for utilizing the anodic oxidation device single stage method to prepare titanic oxide nano compound material according to claim 4 is characterized in that, NH in the said electrolytic solution
4The concentration of F is preferably 0.2wt%-0.5wt%, and the percent by volume of water is preferably 3vol%-5vol%.
6. the method for utilizing the anodic oxidation device single stage method to prepare titanic oxide nano compound material according to claim 4 is characterized in that, said solution temperature remains on 30 ℃-50 ℃, and anodizing time is 20h-40h, and anodic oxidation voltage is 55V-68V.
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102766882A (en) * | 2012-08-10 | 2012-11-07 | 华南理工大学 | Manufacture method for chlorine-evolution dimensionally stable anode (DSA) electro-catalytic electrode with three dimensional structure |
| CN102864480A (en) * | 2012-08-31 | 2013-01-09 | 北京工业大学 | Preparation method of titanium dioxide nanotube array with three-dimensional network structure |
| CN102928492A (en) * | 2012-11-14 | 2013-02-13 | 天津精仪博硕科技发展有限公司 | Analytical system for precise preparation and in-situ test of titanium dioxide nanotube array |
| CN103390744A (en) * | 2013-07-22 | 2013-11-13 | 苏州大学 | A preparation method for a membrane electrode used for a microbattery, the membrane electrode and the microbattery |
| CN103526263A (en) * | 2013-10-21 | 2014-01-22 | 电子科技大学 | Preparation method of Cr-doped TiO2 nanometer magnetic film with room-temperature ferromagnetic effect |
| RU2631780C1 (en) * | 2016-11-07 | 2017-09-26 | Федеральное государственное бюджетное образовательное учреждение высшего образования "Рязанский государственный радиотехнический университет" | Production method of coatings, based on nanoporous titanium dioxide |
| CN108275811A (en) * | 2018-01-10 | 2018-07-13 | 东北石油大学 | A method of passing through the hot THM coupling degradation of organic waste water of optical-electronic-using solar energy |
| CN115613102A (en) * | 2022-10-14 | 2023-01-17 | 攀钢集团攀枝花钢铁研究院有限公司 | Preparation method of anti-pollution oxide film on pure titanium surface |
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Cited By (13)
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| CN102766882A (en) * | 2012-08-10 | 2012-11-07 | 华南理工大学 | Manufacture method for chlorine-evolution dimensionally stable anode (DSA) electro-catalytic electrode with three dimensional structure |
| CN102766882B (en) * | 2012-08-10 | 2015-07-29 | 华南理工大学 | A kind of preparation method analysing chlorine DSA electro catalytic electrode of three-dimensional structure |
| CN102864480B (en) * | 2012-08-31 | 2015-03-04 | 北京工业大学 | Preparation method of titanium dioxide nanotube array with three-dimensional network structure |
| CN102864480A (en) * | 2012-08-31 | 2013-01-09 | 北京工业大学 | Preparation method of titanium dioxide nanotube array with three-dimensional network structure |
| CN102928492A (en) * | 2012-11-14 | 2013-02-13 | 天津精仪博硕科技发展有限公司 | Analytical system for precise preparation and in-situ test of titanium dioxide nanotube array |
| CN103390744A (en) * | 2013-07-22 | 2013-11-13 | 苏州大学 | A preparation method for a membrane electrode used for a microbattery, the membrane electrode and the microbattery |
| CN103390744B (en) * | 2013-07-22 | 2016-01-20 | 苏州大学 | A kind of preparation method of micro cell membrane electrode and membrane electrode and micro cell |
| CN103526263A (en) * | 2013-10-21 | 2014-01-22 | 电子科技大学 | Preparation method of Cr-doped TiO2 nanometer magnetic film with room-temperature ferromagnetic effect |
| CN103526263B (en) * | 2013-10-21 | 2016-02-03 | 电子科技大学 | There is the Cr doped Ti O of room temperature ferromagnetic effect 2the preparation method of nano-magnetic thin films |
| RU2631780C1 (en) * | 2016-11-07 | 2017-09-26 | Федеральное государственное бюджетное образовательное учреждение высшего образования "Рязанский государственный радиотехнический университет" | Production method of coatings, based on nanoporous titanium dioxide |
| CN108275811A (en) * | 2018-01-10 | 2018-07-13 | 东北石油大学 | A method of passing through the hot THM coupling degradation of organic waste water of optical-electronic-using solar energy |
| CN108275811B (en) * | 2018-01-10 | 2021-02-09 | 东北石油大学 | Method for degrading organic wastewater by solar energy through photo-electric-thermal three-field coupling |
| CN115613102A (en) * | 2022-10-14 | 2023-01-17 | 攀钢集团攀枝花钢铁研究院有限公司 | Preparation method of anti-pollution oxide film on pure titanium surface |
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Application publication date: 20120704 |