CN100595336C - Electrochemical industrial titanium anode with oxide seed layer - Google Patents
Electrochemical industrial titanium anode with oxide seed layer Download PDFInfo
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- CN100595336C CN100595336C CN200610135245A CN200610135245A CN100595336C CN 100595336 C CN100595336 C CN 100595336C CN 200610135245 A CN200610135245 A CN 200610135245A CN 200610135245 A CN200610135245 A CN 200610135245A CN 100595336 C CN100595336 C CN 100595336C
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- titanium
- oxide seed
- oxide
- seed layer
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Abstract
The invention discloses an electrochemical industrial titanium anode with oxide seed layer, which is characterized by the following: depositing to cover oxide seed layer on the titanium base of titanium anode; coating subsequent coating layer on the exterior layer of oxide seed layer.
Description
Technical field
The present invention relates to a kind of electrode materials of main Applied Electrochemistry industrial circle, be specifically related to a kind of electrochemical industrial titanium anode that has oxide seed layer.
Background technology
The early stage electrode materials that uses of electrochemistry is a synthetic graphite.After the metal oxide containing precious metals electrode came out in 1967, Graphite Electrodes was replaced by it gradually.The successful prescription of the metal oxide containing precious metals electrode of Chu Xianing is a Ru-Ti oxide compound lining titanium anode the earliest.In order to obtain the electrode materials of high reactivity and high anti-corrosion, the scientific worker has proposed to have the electrochemistry titanium anode [Shao Yanqun etc., " electrochemical industrial titanium anode that has Seed Layer ", 031158463] of Seed Layer.This titanium anode that has meticulous Seed Layer, seed is deposited on the titanium base material, and seed is precious metal or the precious metal chemical complex with nanoscale, can be protective layer or the activation top layer of containing precious metal element on the Seed Layer.But this kind titanium anode cost is higher.
Summary of the invention
The object of the invention provides a kind of electrochemical industrial titanium anode that has oxide seed layer, and such oxide seed can obviously improve titanium anodic over-all properties, and cost is lower.
Content of the present invention is the electrochemical industrial titanium anode that has oxide seed layer, is coated with oxide seed layer in titanium anodic titanium substrate surface deposition, and the outside surface of oxide seed layer is coated with follow-up coating.
Advantage of the present invention is: one: oxide seed is by influencing the forming core and the growth of crystal grain of activated coating, make that the distribution and the density in active centre of coating is changed, thereby further improve electrode performance, the crystalline structure of oxide compound can play the effect of guiding to the forming core of the crystal grain of activated coating; And adopt base metal oxide can also reduce the consumption of precious metal, reduce cost.Two: the present invention has the electrochemical industrial titanium anode of oxide seed layer, the special base metal oxide seed that adopts with rutile structure, can influence follow-up grain shaped nuclear process, process of growth with coating of rutile structure, influence the crystal particle scale of active coating inside, make that the distribution and the density in active centre of the follow-up coating of electrode will be controlled, titanium anodic over-all properties is improved.
Description of drawings
Fig. 1 be at the titanium base material deposited SnO
2-CeO
2The scanning electron microscopy of seed resembles, 50K *
Fig. 2 be at the titanium base material deposited NbO
2The scanning electron microscopy of seed resembles, 50K *
Fig. 3 TiO
2The graphic representation of the active influence of seed oxidation temperature counter electrode
Fig. 4 TiO
2The graphic representation of the influence of seed oxidation temperature counter electrode erosion resistance
Embodiment
General thought and concrete measure that the present invention adopts are, the crystalline structure of oxide seed is identical with the crystalline structure of follow-up coating, then can obviously influence follow-up coating grain shaped nuclear process, process of growth, make that the distribution and the density in active centre of the follow-up coating of electrode is controlled.Because what the follow-up coating (comprising activated coating and protective coating) of most electrode adopted is the coating with rutile structure, therefore can adopt the metal oxide with rutile structure is seed.Rutile belongs to tetragonal system, point group 4/mmm, spacer P4/mnm, O in its structure
2-Ion is made the hexagonal closest packing of distortion, and 4 valence metal ions are on the structure cell summit and the position, body-centered, O
2-Ion face diagonal direction of bottom surface on structure cell respectively has 2, also has 2 in structure cell half another high face diagonal direction.TiO
2It is typical rutile-type structure.Other oxide compound with rutile structure also has SnO
2, MnO
2, PbO
2, VO
2, ZrO
2, NbO
2Deng.Contrast by experiment, the metal oxide with rutile structure of the follow-up coating of energy remarkably influenced has: TiO
2, SnO
2, NbO
2, TiO
2-CeO
2, TiO
2-SnO
2, SnO
2-NbO
2, SnO
2-CeO
2, the metal oxide seed that these have rutile structure can make titanium anodic over-all properties be able to obvious raising.
The electrochemical industrial titanium anode that has oxide seed layer, can obtain by following preparation process: (1) titanium base is handled, and promptly the titanium base material removes ester, deoils with clean-out system, pickling, etching; (2) the seed deposition can adopt electroless plating or physical chemistry sedimentation to add oxide treatment, and practical is sol-gel method and thermal decomposition method, depositing Ti O on the titanium base material
2, SnO
2, NbO
2, TiO
2-CeO
2, TiO
2-SnO
2, SnO
2-NbO
2, SnO
2-CeO
2Deng the discrete particles oxide seed; Seed has 4～20nm nanoscale; Seed in the Seed Layer has 50～80% titanium base coverage; (3) follow-up coating is handled, and can adopt sol-gel method and thermal decomposition method, and deposition contains the metal or the oxide compound subsequent deposition layer (comprising activated coating or protective layer) of precious metal element, and outermost layer is the active surface.
Wherein, the oxide seed layer seed of electrochemical industrial titanium anode can be a base metal oxide; Seed is to have the oxide particle that nanoscale is 4～20nm; Seed can be TiO
2, SnO
2, NbO
2, TiO
2-CeO
2, TiO
2-SnO
2, SnO
2-NbO
2, SnO
2-CeO
2Oxide seed, this oxide seed are deposited on the titanium base material, and it has 50～80% titanium base coverage; The crystalline structure of seed is identical with the crystalline structure of follow-up coating.
Can adopt the metal oxide with rutile structure is seed.
Follow-up coating is activated coating or the protective layer that contains precious metal.
Below narrate two embodiment of the present invention
Embodiment 1
Preparation has SnO
2-CeO
2Oxide seed to contain the titanium anode that ru oxide is the active surface.The titanium anode of its oxide seed layer between titanium base material and active surface.
Concrete steps are: (1) is 5cm with thickness for the 1mm area
2The TA1 titanium-base after with the washing of 5% washing powder solution, digestion is 2 hours in 20% hydrochloric acid soln, washing then, drying.(2) in Sn: the Ce mol ratio is 91: 9 a ratio, takes by weighing SnCl
4And Ce (NO
3)
2, respectively it is dissolved in ethanol, press citric acid and Sn
4+And Ce
2+3: 1 ratio of one-tenth mol ratio is added citric acid, is mixed with to contain Sn
4+And Ce
2+Total content is the Sn-Ce citric acid sol paint of 10g/L.(3) Sn-Ce citric acid colloidal sol is coated on the titanium-base, in retort furnace,, obtains SnO through 450 ℃ of oxide treatment 1 hour
2-CeO
2Oxide seed modification titanium base material, its surface topography as shown in Figure 1.(4) will have SnO
2-CeO
2The titanium-base of the oxide seed layer ruthenium trichloride of 26mol/L and the titanous chloride ethanolic soln brushing of 78mol/L, expose to curing with infrared light, 450 ℃ of down calcining, oxidations 1 hour in retort furnace then, 6 times repeatedly, annealed 1 hour down at 450 ℃ at last, obtain to have SnO
2-CeO
2Oxide seed to contain the titanium anode that ru oxide is the active surface.
For the ease of contrast, do not have oxide seed, have SnO
2Oxide seed and have a CeO
2Oxide seed be that active surface's titanium anode is also used method for preparing to contain ru oxide.In the sulphuric acid soln of 1mol/L, with 1A/cm
2The quick electrolysis of current density detects and shows, has SnO
2-CeO
2Oxide seed titanium anode is compared with the titanium anode with oxide seed not, and their electro catalytic activity is close.But the erosion resistance of electrode that has oxide seed is more superior.
Table 1 oxide seed layer is to the influence of titanium anode performance
| Titanium anode kind | Chlorine evolution potential (V) | Reinforcing life (min) |
| No Seed Layer band SnO 2Plant subband CeO 2Plant subband SnO 2-CeO 2Seed | 1.111 1.111 1.112 1.112 | 600 720 670 815 |
Embodiment 2
Preparation has TiO
2Oxide seed to contain the titanium anode that iridium oxide is the active surface.
Concrete steps are: the area of (1) thick 1mm is 4cm
2The TA2 titanium-base after degrease washing, digestion is 2 hours in 10% oxalic acid solution, washing then, drying.(2) take by weighing TiCl
3It is dissolved in ethanol, obtains the TiCl of 1mol/L
3Ethanolic soln is pressed citric acid and Ti
3+Form 3: 1 ratio of mol ratio and add citric acid, be mixed with Ti
3+Content is the titaniferous citric acid coating of 10g/L.(3) this sol paint is coated on the titanium-base, through 450 ℃～600 ℃ differing tempss, oxidizing thermal treatment 1 hour is to obtain TiO in retort furnace
2Oxide seed modification titanium base material.(4) be that 34.9% chloro-iridic acid is a raw material with containing the iridium massfraction, be dissolved in the chloro-iridic acid ethanol masking liquid that ethanol preparation gets 1mol/L, the titanium-base that will have Seed Layer is brushed, and extremely solidifies with infra-red light irradiation, 500 ℃ of calcinings down in retort furnace then, oxidation 1 hour.Repeatable operation repeatedly makes the amount of coating of iridium reach 4g/m
2Annealed 1 hour down at 450 ℃ at last, obtain to have TiO
2One group of oxide seed to contain the titanium anode that iridium oxide is the active surface.
In order to obtain best effect, the prepared titanium anode sample through heat treatments at different is carried out performance test.The results are shown in Figure 3 and Fig. 4.From Fig. 3 as seen, oxidizing temperature is too low, and the seed oxidation is insufficient; Oxidizing temperature is too high, and damage appears in the titanium base material; Sample through 300～550 ℃ of following oxidations has the very high oxygen activity of analysing.From Fig. 4 as seen, oxidizing temperature is too low or too high, and corrosion resistance nature is all bad; Sample through 450～550 ℃ of following oxidations has very high corrosion resistance nature.
Claims (6)
1. electrochemical industrial titanium anode that has oxide seed layer, it is characterized in that: described titanium anodic titanium substrate surface deposition is coated with oxide seed layer, the outside surface of oxide seed layer is coated with follow-up coating, the concrete preparation process of described titanium anodic is: (1) with the TA1 titanium-base after with the washing of 5% washing powder solution, digestion is 2 hours in 20% hydrochloric acid soln, washing then, drying; (2) in Sn: the Ce mol ratio is 91: 9 a ratio, takes by weighing SnCl
4And Ce (NO
3)
2Respectively it is dissolved in ethanol, presses citric acid and Sn
4+And Ce
2+Total content becomes 3: 1 ratio of mol ratio to add citric acid, is mixed with to contain Sn
4+And Ce
2+Total content is the Sn-Ce citric acid sol paint of 10g/L; (3) Sn-Ce citric acid colloidal sol is coated on the titanium-base, in retort furnace,, obtains SnO through 450 ℃ of oxide treatment 1 hour
2-CeO
2Oxide seed modification titanium base material; (4) will have SnO
2-CeO
2The titanium-base of the oxide seed layer ruthenium trichloride of 26mol/L and the titanous chloride ethanolic soln brushing of 78mol/L, expose to curing with infrared light, 450 ℃ of down calcining, oxidations 1 hour in retort furnace then, 6 times repeatedly, annealed 1 hour down at 450 ℃ at last, obtain to have SnO
2-CeO
2Oxide seed to contain the titanium anode that ru oxide is the active surface.
2. electrochemical industrial titanium anode that has oxide seed layer, it is characterized in that: described titanium anodic titanium substrate surface deposition is coated with oxide seed layer, the outside surface of oxide seed layer is coated with follow-up coating, the concrete preparation process of described titanium anodic is: (1) TA2 titanium-base is after the degrease washing, digestion is 2 hours in 10% oxalic acid solution, washing then, drying; (2) take by weighing TiCl
3It is dissolved in ethanol, obtains the TiCl of 1mol/L
3Ethanolic soln is pressed citric acid and Ti
3+Form 3: 1 ratio of mol ratio and add citric acid, be mixed with Ti
3+Content is the titaniferous citric acid coating of 10g/L; (3) this sol paint is coated on the titanium-base, through 450 ℃～600 ℃ differing tempss, oxidizing thermal treatment 1 hour is to obtain TiO in retort furnace
2Oxide seed modification titanium base material; (4) be that 34.9% chloro-iridic acid is a raw material with containing the iridium massfraction, be dissolved in the chloro-iridic acid ethanol masking liquid that ethanol preparation gets 1mol/L, the titanium-base that will have Seed Layer is brushed, extremely solidify with infra-red light irradiation, 500 ℃ of calcinings down in retort furnace then, oxidation 1 hour, repeatable operation repeatedly make the amount of coating of iridium reach 4g/m
2Annealed 1 hour down at 450 ℃ at last, obtain to have TiO
2One group of oxide seed to contain the titanium anode that iridium oxide is the active surface.
3. the electrochemical industrial titanium anode that has oxide seed layer according to claim 1 and 2 is characterized in that: the seed in the described oxide seed layer is to have the oxide particle that nanoscale is 4～20nm.
4. the electrochemical industrial titanium anode that has oxide seed layer according to claim 1 and 2 is characterized in that: described oxide seed is deposited on the titanium base material, and it has 50～80% titanium base coverage.
5. the electrochemical industrial titanium anode that has oxide seed layer according to claim 1 and 2 is characterized in that: the crystalline structure of described follow-up coating is identical with the crystalline structure of oxide seed.
6. the electrochemical industrial titanium anode that has oxide seed layer according to claim 1 and 2 is characterized in that: the crystalline structure of described oxide seed is a rutile structure.
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| CN100595336C true CN100595336C (en) | 2010-03-24 |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101289750B (en) * | 2008-06-13 | 2010-09-29 | 福州大学 | Titanium anodic of nano TiO2 seed coating and method for preparing same |
| CN102392268B (en) * | 2011-11-08 | 2014-03-12 | 福州大学 | Silver coating adopting substrate modified by active oxides and preparation method thereof |
| CN102677092B (en) * | 2012-05-30 | 2015-01-14 | 浙江大学 | Preparation method of titanium anode |
| CN103556133B (en) * | 2013-11-05 | 2015-07-01 | 福州大学 | Transition-layer-introduced modified titanium substrate conducting coating and preparation method thereof |
| CN107779847B (en) * | 2017-09-25 | 2018-11-02 | 上海同臣环保有限公司 | A kind of coating titanium anode and its spray pyrolysis preparation method |
| CN110104739B (en) * | 2019-05-27 | 2022-02-11 | 中国华能集团清洁能源技术研究院有限公司 | Efficient electrode for treating industrial circulating cooling water and preparation method thereof |
| CN114369824B (en) * | 2021-12-31 | 2023-03-14 | 海南大学 | Method for preparing DSA electrode by hydrothermally growing RuO2 or IrO2 on titanium surface by using seed crystal method |
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Non-Patent Citations (6)
| Title |
|---|
| 纳米二氧化钛系材料的合成及表征技术. 叶超群，孟中岩.陶瓷学报，第23卷第3期. 2002 |
| 纳米二氧化钛系材料的合成及表征技术. 叶超群，孟中岩.陶瓷学报，第23卷第3期. 2002 * |
| 钛基纳米二氧化钛电极的电催化性能及在电合成对氨基苯酚中的应用. 程磊.郑州大学硕士学位论文. 2006 |
| 钛基纳米二氧化钛电极的电催化性能及在电合成对氨基苯酚中的应用. 程磊.郑州大学硕士学位论文. 2006 * |
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