CN1284883C - Electro-chemical industrial titanium anode with seed layer - Google Patents
Electro-chemical industrial titanium anode with seed layer Download PDFInfo
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- CN1284883C CN1284883C CN 03115846 CN03115846A CN1284883C CN 1284883 C CN1284883 C CN 1284883C CN 03115846 CN03115846 CN 03115846 CN 03115846 A CN03115846 A CN 03115846A CN 1284883 C CN1284883 C CN 1284883C
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Abstract
The present invention describes a titanium anode with a fine seed layer, which is suitable for electrochemical industry. Seeds are deposited on a titanium substrate and are nanometer noble metal or noble metal compounds, a protecting layer or an activating surface layer can be arranged on the seed layer, wherein the protective layer or the active surface layer contains noble metal elements, and the seed layer is at least arranged between the titanium substrate and the active coating. According to the research results for improving the activity of electrode materials, the activity of the electrode materials is relevant to the active center of a surface. Under the condition of a certain number of active substances, the higher the density of the active center is, the higher the activity of the electrode is. In the present invention, fine seed grains are firstly deposited on the substrate, a uniform, disperse or dense coating can be obtained and the result is that the activity of the electrode is improved. The seeds are deposited on the titanium substrate and are the nanometer noble metal or noble metal compounds, and the protective layer or the active surface layer can be arranged on the seed layer, wherein the protective layer or the active surface layer contains noble metal elements. The present invention provides an effective measure for the solution of the defects of the prior art.
Description
Technical field:
The present invention relates to a kind of electrochemical industrial titanium anode that has Seed Layer, promptly a kind of main Applied Electrochemistry industrial circle has the electrode materials of novel texture.Its Application Areas comprises chlorine industry, oxymuriate industry, clorox industrial production, cathodic protection, electroplating industry etc., need to be specially adapted to high anti-corrosion occasion.
Background technology:
By retrieval as can be known: the early stage electrode materials that uses of electrochemistry is a synthetic graphite.After metal oxide containing precious metals 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 Ru30%-Ti70% oxide compound lining titanium anode the earliest.In order to obtain the electrode materials of high reactivity and high anti-corrosion, the scientific worker proposes to adopt the titanium anode of protective layer structure.It is the titanium anode of protective layer with the platinum metals that U.S. Pat 3663414 has proposed.Add the purpose of protective layer in order that will stop the further oxidation in the process under arms of titanium base material.In order to utilize protective layer to attach to improve the activity of electrode, United States Patent (USP) (US4213843, US4331528) and Japanese Patent have proposed employing respectively quite active oxide compound iridium, iridium-ruthenium and iridium-rhodium-ru oxide are arranged have been the titanium anode of protective layer.(patent No.: also proposing 87105832) with iridium-cobalt/cobalt oxide is the titanium anode of protective layer at Chinese patent in this research group.Though these titanium anodes play obvious effects improving on the titanium anodic solidity to corrosion, because the first-selected performance of using as electrode of material is active, and above-mentioned electrode materials does not play obvious effects aspect active improving.
According to the result of study that improves electrode material activity, the activity of electrode materials is relevant with the active centre on surface, and under a certain amount of active substance condition, active centre density is high more, and then electrode activity is high more.This just provides effective measure for addressing the deficiencies of the prior art.In addition, if improve the protection effect of protective layer, the inside crystal grain of protective layer is tiny more, and then structure is fine and close more, and the ability of its protection infiltration will be strong more.Therefore, the inventor thinks the titanium anode that adopts a kind of novel texture, promptly on base material, deposit meticulous seed grain earlier, the seed that disperse distributes influenced follow-up coating grain shaped nuclear process, process of growth, influenced 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.For this reason, obtain evenly, disperse or fine and close coating will realize that the result will make the activity of electrode be improved.
Summary of the invention:
The objective of the invention is to develop a kind of electrochemical industrial titanium anode that has Seed Layer.
Task of the present invention is to adopt a kind of titanium anode of novel texture, contains Seed Layer between titanium basic unit and activated coating at least.The titanium anode that promptly has meticulous Seed Layer, seed are 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.
Description of drawings:
Below in conjunction with accompanying drawing the present invention is further described:
Fig. 1 is the weave construction synoptic diagram of the electrode materials of seed of the present invention between base material and active surface;
Fig. 2 is the weave construction synoptic diagram of the electrode materials of seed of the present invention between base material and protective layer.
Among the figure: 1 is titanium basic unit; 2 is Seed Layer; 3 is activated coating; 4 is protective layer.
On the basis of above analysis and further experimental verification, the inventor has proposed a kind of titanium anode of novel texture, and the weave construction of titanium anode material schematically is depicted in Fig. 1.Its inventive point mainly is the crucial constituting body of the titanium anode material that becomes of Seed Layer, wherein 1) and 2) be respectively Seed Layer at the titanium anode between titanium base material and the active surface and between titanium base material and protective layer.Seed can be selected different element kinds, different compounds and different lattice dot matrix according to the character of follow-up coating.But key is that it has meticulous nanoscale.Therefore, seed can be the precious metal or the precious metal chemical complex of nanoscale.Can be protective layer or the activation top layer of containing precious metal element on the Seed Layer.Be at activated coating 3 and the Seed Layer 2 middle protective layers 4 that add as can be known among Fig. 2.
The titanium anode preparation process of this novel texture can experience usually: 1) the 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 physical deposition, electroless plating or physical chemistry sedimentation, is preferably chemical deposition.Seed in the Seed Layer 2 is to have metal or the compound particle that nanoscale is 4～30nm.Seed in the Seed Layer (2) is precious metal or metal oxide containing precious metals particle.Seed in the Seed Layer 2 is deposited on the titanium basic unit 1, and it has the titanium base coverage of 50-80%.3) follow-up coating is handled, and can be plating, electroless plating or other wet chemical methods, is preferably thermal decomposition method.Activated coating 3 is metal or the oxide compound subsequent deposition layers that contain precious metal element with protective layer 4.Activated coating 3 is active surfaces of containing the metal or the oxide compound of precious metal element with protective layer 4.
Below be described in detail two embodiment of the present invention:
Embodiment one:
Preparation has the titanium anode with double-layer structure of nano level metal ruthenium seed, the titanium anode of its Seed Layer between titanium base material and active surface.Concrete steps are: the area of (1) thick 1mm be the TA1 of 5cm2 after with the washing of 5% washing powder solution, digestion is 2 hours in 20% hydrochloric acid soln, washing then, drying.(2) treated titanium base material in containing the 10% trioctylamine kerosin that ruthenium is 500ppm under intensive stirs immersion plating 5min, in industrial acetone, clean up after the immersion plating, dry up.(3) titanium-base that will have a Seed Layer with contain 50 and ruthenium trichloride and the titanous chloride ethanolic soln of 150g/l brush, solidify with infrared(ray)lamp, then in retort furnace, in 300-500 ℃ of calcining down, oxidation.Repeatable operation repeatedly makes the amount of coating of ruthenium reach 8g/m
2After testing, the electrode activity top layer that has a Seed Layer has meticulousr crystalline-granular texture (seeing Table 1).
Table 1 Seed Layer is to the influence of active surface's crystal particle scale
| Titanium anode kind | Seed category | Seed yardstick (nm) | Active surface's composition | Grain-size (nm) |
| No Seed Layer has Seed Layer | -metal Ru | - 10～15 | (Ti，Ru)O2 (Ti，Ru)O2 | 30～50 20～30 |
Embodiment two:
Preparation has the titanium anode with three-decker of nano level metal ruthenium seed, the titanium anode of its Seed Layer between titanium base material and protective layer.Concrete steps are: the area of (1) thick 1mm is 5cm
2TA1 after with the washing of 5% washing powder solution, digestion is 2 hours in 20% hydrochloric acid soln, washing then, drying.(2) treated titanium base material in containing the 10% trioctylamine kerosin that ruthenium is 500ppm under intensive stirs immersion plating 5min, in industrial acetone, clean up after the immersion plating, dry up, and at 400 ℃ of calcining 10min down.(3) titanium-base that will have Seed Layer is brushed with the iridous chloride ethanolic soln that contains 10g/l, solidifies with infrared(ray)lamp, then in retort furnace, in 300-500 ℃ of calcining down, oxidation.Repeatable operation repeatedly makes the amount of coating of iridium reach 2g/m2.Acquisition has the protective layer of meticulous crystalline-granular texture.(4) titanium-base that will have a protective layer with contain 50 and ruthenium trichloride and the titanous chloride ethanolic soln of 150g/l brush, solidify with infrared(ray)lamp, then in retort furnace, in 300-500 ℃ of calcining down, oxidation.Repeatable operation repeatedly makes the amount of coating of ruthenium reach 8g/m
2After testing, the electrode activity top layer that has a Seed Layer has meticulousr crystalline-granular texture (seeing Table 2).
Table 1 Seed Layer is to the influence of active surface's crystal particle scale
| Titanium anode kind | Seed category | Seed yardstick (nm) | The protective layer composition | Grain-size (nm) |
| No Seed Layer has Seed Layer | - RuO2 | - 15～25 | IrO2 IrO2 | 30～50 20～30 |
Claims (5)
1. have the electrochemical industrial titanium anode of Seed Layer, it is characterized in that: contain Seed Layer (2) at least between titanium basic unit (1) and activated coating (3), the seed in the Seed Layer (2) is deposited on the titanium basic unit (1), and it has the titanium base coverage of 50-80%.
2. the electrochemical industrial titanium anode that has Seed Layer according to claim 1 is characterized in that: at the middle protective layer (4) that adds of activated coating (3) and Seed Layer (2).
3. the electrochemical industrial titanium anode that has Seed Layer according to claim 1 is characterized in that: the seed in the Seed Layer (2) is to have metal or the compound particle that nanoscale is 4～30nm.
4. the electrochemical industrial titanium anode that has Seed Layer according to claim 1 is characterized in that: the seed in the Seed Layer (2) is precious metal or metal oxide containing precious metals particle.
5. according to the arbitrary described a kind of electrochemical industrial titanium anode that has Seed Layer of claim 1 to 4, it is characterized in that: activated coating (3) is metal or the oxide compound that contains precious metal element with protective layer (4).
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| CN 03115846 CN1284883C (en) | 2003-03-11 | 2003-03-11 | Electro-chemical industrial titanium anode with seed layer |
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| CN 03115846 CN1284883C (en) | 2003-03-11 | 2003-03-11 | Electro-chemical industrial titanium anode with seed layer |
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| CN1438362A CN1438362A (en) | 2003-08-27 |
| CN1284883C true CN1284883C (en) | 2006-11-15 |
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| CN 03115846 Expired - Fee Related CN1284883C (en) | 2003-03-11 | 2003-03-11 | Electro-chemical industrial titanium anode with seed layer |
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Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102839387A (en) * | 2012-09-20 | 2012-12-26 | 福州大学 | Titanium anode having Ru-Ir-Ti ternary coating with embedded structure and preparation method thereof |
| CN110438527A (en) * | 2019-08-05 | 2019-11-12 | 上海氯碱化工股份有限公司 | The preparation method of the transient metal doped anode containing ruthenium coating |
| CN112195482B (en) * | 2020-10-15 | 2023-05-16 | 昆明冶金研究院有限公司 | Composite titanium anode plate 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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