CN103774175A - Ruthenium zirconium tin titanium oxide-embedded active coating and preparation method thereof - Google Patents
Ruthenium zirconium tin titanium oxide-embedded active coating and preparation method thereof Download PDFInfo
- Publication number
- CN103774175A CN103774175A CN201410037157.1A CN201410037157A CN103774175A CN 103774175 A CN103774175 A CN 103774175A CN 201410037157 A CN201410037157 A CN 201410037157A CN 103774175 A CN103774175 A CN 103774175A
- Authority
- CN
- China
- Prior art keywords
- titanium oxide
- zirconium tin
- tin titanium
- ruthenium zirconium
- ruthenium
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Landscapes
- Inert Electrodes (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
The invention discloses a ruthenium zirconium tin titanium oxide-embedded active coating and a preparation method thereof. The active coating uses iridium tantalum oxide as the main body into which ruthenium zirconium tin titanium oxide is embedded. The preparation method comprises the following steps: controlling the sintering temperature to obtain the nano ruthenium zirconium tin titanium oxide powder of which the size is less than 10nm; and mixing the nano ruthenium zirconium tin titanium oxide powder into an iridium tantalum oxide precursor, thermosetting, and carrying out oxidation sintering and annealing in a box type furnace at 520 DEG C to obtain the embedded iridium tantalum oxide active coating. The active material has the property of precipitating oxygen and chlorine, obviously enhances the comprehensive activity of the iridium tantalum active oxide coating, and has higher practicality. The preparation method is simple and convenient, and has the characteristics of high operability and high cost performance.
Description
Technical field
The electrode materials field that the invention belongs to Applied Electrochemistry and energy industry, relates to a kind of material with high electrocatalysis characteristic and preparation method thereof.Concrete Application Areas comprises electrochemistry parts and the devices such as acid electrolytic solution, weak brine electrolysis, organic solution electrolysis, cathodic protection, electrochemical sensor.Suitablely especially be used as the activated coating of electrode materials in analysing electrolyzer chlorine, oxygen are two.
Background technology
Active electrode is parts crucial in electrochemical industry, and nineteen sixty-five Beer develops ruthenium dioxide coated anode first, has opened up anode material of new generation, the existence of activated coating give this class anode high analyse chlorine activity.Through large quantity research, in activated coating, with RuO
2+ TiO
2the binary oxide being composited has more superior over-all properties, is to analyse the industrial coated material the most generally adopting of chlorine.People recognize gradually, and ruthenium dioxide coating is not adapted at analysing in the occasion of oxygen and applies.Vercesi in 1991 etc. have proposed to adopt iridium base oxide can realize the demand of oxygen evolution reaction, have succeeded in developing IrO later
2+ Ta
2o
5composite oxides anode material, this material can be applicable to more harsh electrolytic condition, and has higher oxygen evolution activity.At present, analyse chlorine and analyse oxygen electrode and become topmost two class gassing active electrode materials in electrochemical industry.Along with industrial expansion, the expansion of Application Areas, the complexity of environment for use, the traditionally single Cl that analyses
2, analyse O
2day by day highlight by the limitation of anode.As in electrometallurgy field, the electrolytic acid aqueous solution and perchlorate are produced, more situation is to exist containing oxygen and chlorine-containing compound in electrolytic solution, makes electrolytic environments more harsh, and therefore electrode materials is also subject to more acid test.For this reason, research and development oxygen, chlorine is two analyses electrode materials and has very important practical significance.For the activated coating of development of new, this research team is round TiO
2+ RuO
2and IrO
2+ Ta
2o
5conduct in-depth research, obtained certain achievement, as in 91 volumes of 2008 " U.S. pottery association journal " with " Phase Structure and Microstructure of a Nanoscale TiO
2-RuO
2-IrO
2-Ta
2o
5anode Coating on Titanium " for topic, disclose a kind of TiO
2+ RuO
2+ IrO
2+ Ta
2o
5the technology of preparing of activated coating; In Chinese patent 200810072273.1, propose the patent of invention that adopts the activity of alternating structure " to there is the preparation method of the titanium anode of alternating structure coating ", obtained patent for invention.These coatings play obvious effect in the solidity to corrosion of improving titanium anode.Recently, it is the method for oxide compound that the research of this research group finds to adopt embedding ruthenium, and more can realize ruthenium system and iridium is the regulation and control of active substance and performance.At IrO
2-Ta
2o
5in coating oxidation thing, add RuO
2-ZrO
2-SnO
2-TiO
2the method of oxide nanocrystalline, improves IrO
2+ Ta
2o
5analyse chlorine characteristic, prepare a kind of iridium tantalum active anode coating of damascene structures of novel ruthenium zirconium tin titanium oxide, can obtain the characteristic of simultaneously analysing oxygen and analyse chlorine, thereby can obtain efficient oxygen, the two activated coating electrode materialss of analysing of chlorine.
Summary of the invention
The object of this invention is to provide a kind of activated coating that embeds ruthenium zirconium tin titanium oxide and preparation method thereof, thereby obtain the high reactivity electrode materials that has stronger pervasive effect.
Thinking of the present invention is in original iridium tantalum pentoxide activated coating, utilizes embedded technology in this coating, to add ruthenium zirconium tin titanium oxide, can analyse at the same time oxygen and analyse and in chlorine occasion, have more superior activity to improve iridium tantalum pentoxide.This thinking is to be respectively analysing chlorine and analysing two the most frequently used class active electrode materials of oxygen of generally acknowledging at present based on iridium tantalum pentoxide and ruthenium titanium oxide, and we find in nearest research, and ruthenium zirconium tin titanium oxide is the active coated material higher compared with ruthenium titanium oxide.Along with growing industrial expansion, the expansion of Application Areas, the complexity of environment for use, the traditionally single Cl that analyses
2, analyse O
2day by day highlight by the limitation of anode.In order to adapt to this variation, this team has proposed to adopt and in iridium tantalum pentoxide activated coating, has embedded ruthenium zirconium tin titanium oxide, make electrode under arms in process, except the oxygen evolution reaction of iridium tantalum pentoxide, exposedly can analyse chlorine reaction, the effective active of the electrode of enhancing at surperficial ruthenium zirconium tin titanium oxide.This oxygen, chlorine pair are analysed electrode materials and are had very important practical significance.
Principle of operation of the present invention adds the nano level ruthenium zirconium of part tin titanium active oxidation composition granule exactly in iridium tantalum pentoxide presoma.Our recent research finds, the ruthenium zirconium tin titanium oxide of small scale more easily obtains than ruthenium titanium oxide.Described damascene structures is to come from the effect that adopts the insert of about < 10 nm of particle diameter to add, and has the similar structure of matrix material thereby obtained.Pass through again ruthenium zirconium tin titanium oxide nanoscale and the ratio control with iridium tantalum pentoxide, can obtain analysing oxygen and analysing the performance of chlorine of needing.Because the dosage of insert produces obviously impact to the internal organizational structure of active material, add very little, embed interface increasing amount limited, the active effect improving is limited.Add too much, the interface accounting of embedding is too high, affects the associativity of active material, and corrosion resisting property is had a negative impact.Find by research, adopt tiny ruthenium zirconium tin titanium active oxidation composition granule, can make the content of insert improve.Therefore, the molar weight of insert active substance, in the time reaching 25 mol% that is coated with stratum total, can have best over-all properties.
Core technology take the nanocrystalline iridium tantalum activating oxide coating as insert of ruthenium zirconium tin titanium oxide prepared by employing embedding inlay technique of the present invention comprises, (1) first prepares ruthenium zirconium tin titanium oxide, and it has suitable nanoscale; (2) mix with the presoma of iridium tantalum activating oxide, on common deposition and titanium base material; (3) thermal treatment of the iridium tantalum pentoxide coating that contains ruthenium zirconium tin titanium oxide embedded structure.
Preparation method of the present invention mainly comprises following four steps:
(1) preparation of ruthenium zirconium tin titanium oxide slurries: with RuCl
3, ZrCl
4, SnCl
4and TiCl
3for source material, take each source material by Ru:Zr:Sn:Ti certain proportion, they are mixed, obtain ruthenium zirconium tin titanium oxide active slurry;
(2) sintering of ruthenium zirconium tin titanium oxide nanoparticles preparation: extract ruthenium zirconium tin titanium oxide active slurry, after being heating and curing, then oxidation and sinter, acquisition has the insert of the ruthenium zirconium tin titanium oxide of nanoscale.
(3) preparation of iridium tantalum pentoxide slurries: with H
2irCl
6and TaCl
5for source material, take in proportion each source material, the two is mixed, obtain active slurry;
(4) preparation of activated coating: ruthenium zirconium tin titanium oxide nanoparticles is sneaked in iridium tantalum pentoxide active slurry, fully stir, be coated on titanium base material; after being heating and curing; oxidation and sinter, finally annealing, obtains the iridium tantalum pentoxide active coated Ti that embeds ruthenium zirconium tin titanium oxide.
Remarkable advantage of the present invention is:
(1) the present invention has effectively utilized the principle of the increase crystal boundary ratio of nanotechnology and matrix material, imports a large amount of damascene structures by embedding grammar.Increase the number of channels of proton, thereby the activity of electrode materials is improved.
(2) due to by the nano-powder of the fine dimension of the dispersion that has of preparation in advance, after embedding, make the crystal miniaturization of final ruthenium zirconium tin titanium oxide, increase the density in active centre, thereby the actual bearer current density at electrode activity center is declined, thereby the activity of electrode materials is improved.
(3) owing to adding the nano level ruthenium zirconium of part tin titanium active oxidation composition granule in iridium tantalum pentoxide presoma.Can be by the ratio control of ruthenium zirconium tin titanium oxide and iridium tantalum pentoxide, can obtain analysing oxygen and analysing the performance of chlorine of needing.Because coating of the present invention is take iridium tantalum pentoxide as main, so the activity of its gassing is mainly to analyse oxygen, less important is to analyse chlorine.
(4) the present invention, owing to having adopted traditional ruthenium zirconium tin titanium oxide active slurry to solidify in advance, disperses, the method for refinement, and the making of raw material and storage are all easy to.Added in iridium tantalum active slurry, can be prepared electrode materials by traditional technology.Therefore technique is simple, easily goes, and does not totally make tooling cost increase.Owing to improving the performance of electrode materials, make the cost performance of electrode product be able to obvious improvement.
Accompanying drawing explanation
Fig. 1 is transmission electron microscopy (TEM) photo of ruthenium zirconium tin titanium oxide insert.
Embodiment
The concrete preparation process of the iridium tantalum pentoxide with original position embedded structure of the present invention is as follows:
(1) preparation of ruthenium zirconium tin titanium oxide slurries: with RuCl
3, ZrCl
4, SnCl
4and TiCl
3for source material, be that 3:1:3:3 ratio takes each source material in Ru:Zr:Sn:Ti mol ratio, and be dissolved in respectively butanols, concentration is controlled at 0.3 mol/L left and right, after each source material fully dissolves, they is mixed, and obtains ruthenium zirconium tin titanium oxide active slurry;
(2) sintering of ruthenium zirconium tin titanium oxide nanoparticles preparation: quantitatively extract ruthenium zirconium tin titanium oxide active slurry, after 90 ℃ are heating and curing, take out and grind, then oxidation and sinter in the box-type furnace of 380 ℃, come out of the stove cooling, after grinding, obtain the insert of the ruthenium zirconium tin titanium oxide with nanoscale.
(3) preparation of iridium tantalum pentoxide slurries: with H
2irCl
6and TaCl
5for source material, in Ir: the Ta mol ratio ratio of 65: 35 takes each source material, and is dissolved in respectively butanols, concentration is controlled at 0.2 mol/L left and right, after each source material fully dissolves, the two is mixed, and obtains active slurry;
(4) preparation of activated coating: 25 mol% that press mole total amount of active substance extract the iridium tantalum active slurry of ruthenium zirconium tin titanium oxide nano-powder and 75mol%, ruthenium zirconium tin titanium oxide nanoparticles is sneaked in iridium tantalum pentoxide active slurry, fully stir, be coated on the titanium base material after the 1 hour cleaning-drying of 10% oxalic acid etching that seethes with excitement, after 110 ℃ are heating and curing, oxidation and sinter 10 minutes in the box-type furnace of 520 ℃, after cooling, row applies again, thermal treatment, come out of the stove cooling, repeat altogether 15 times, finally 520 ℃ of annealing 1 hour, obtain the iridium tantalum pentoxide active coated Ti that embeds ruthenium zirconium tin titanium oxide.
The present invention has obtained the iridium tantalum pentoxide active titanium anode that has embedded ruthenium zirconium tin titanium oxide nanostructure by above-mentioned enforcement.Research shows, the increasing of the refinement of crystal grain and crystal boundary, effectively improve activating oxide active centre density, improve the conductive capability of dispersion state and proton, to such an extent as to activity is improved.Because the present invention is to having the iridium tantalum pentoxide active material that embeds ruthenium zirconium tin titanium oxide structure, has and analysed oxygen simultaneously and analyse the activity of chlorine.Carry out contrast experiment with traditional iridium tantalum pentoxide active material of preparing under equal conditions, result shows that the over-all properties of the iridium tantalum pentoxide active material with ruthenium zirconium tin titanium oxide embedded structure is improved significantly.Table 1 is the analysing oxygen and analysing chlorine performance under parallel laboratory test condition without iridium tantalum pentoxide active material embedded structure and that have embedded structure.Can clearly find out, the titanium anode of embedded structure is suitable with the oxygen evolution potential of traditional titanium anode in the performance of analysing oxygen, but its current potential of analysing chlorine obviously reduces.This fully shows, has the iridium tantalum pentoxide active material that embeds ruthenium zirconium tin titanium oxide nanostructure and has good oxygen, the two performances of analysing of chlorine.
Below describe one embodiment of the present of invention in detail, but the present invention is not only limited to this.
Embodiment 1
Adding the preparation of the iridium tantalum activating oxide covering electrodes material of 25mol% insert carries out according to the following steps:
(1) preparation of ruthenium zirconium tin titanium oxide slurries: with RuCl
3, ZrCl
4, SnCl
4and TiCl
3for source material, the ratio that is 3:1:3:3 in Ru:Zr:Sn:Ti mol ratio takes each source material, and is dissolved in respectively butanols, and concentration is controlled at 0.3 mol/L, after each source material fully dissolves, they is mixed, and obtains ruthenium zirconium tin titanium oxide active slurry;
(2) sintering of ruthenium zirconium tin titanium oxide nanoparticles preparation: quantitatively extract ruthenium zirconium tin titanium oxide active slurry, after 90 ℃ are heating and curing, take out and grind, then oxidation and sinter in the box-type furnace of 380 ℃, come out of the stove cooling, after grinding, obtain and there is the insert that nanoscale is the ruthenium zirconium tin titanium oxide of 8 nm.
(3) preparation of iridium tantalum pentoxide slurries: with H
2irCl
6and TaCl
5for source material, in Ir: the Ta mol ratio ratio of 65: 35 takes each source material, and is dissolved in respectively butanols, and concentration is controlled at 0.2 mol/L, after each source material fully dissolves, the two is mixed, and obtains active slurry;
(4) preparation of activated coating: 25 mol% that press mole total amount of active substance extract the iridium tantalum active slurry of ruthenium zirconium tin titanium oxide nano-powder and 75mol%, ruthenium zirconium tin titanium oxide nanoparticles is sneaked in iridium tantalum pentoxide active slurry, fully stir, be coated on the titanium base material of etching, after 110 ℃ are heating and curing, oxidation and sinter 10 minutes in the box-type furnace of 520 ℃, after cooling, row applies again, thermal treatment, come out of the stove cooling, repeat altogether 15 times, finally 520 ℃ of annealing 1 hour, obtain the iridium tantalum pentoxide active coated Ti that embeds ruthenium zirconium tin titanium oxide.
Table 1 has the electrochemical properties of the iridium tantalum pentoxide titanium anode that embeds ruthenium zirconium tin titanium oxide structure
The foregoing is only preferred embodiment of the present invention, all equalizations of doing according to the present patent application the scope of the claims change and modify, and all should belong to covering scope of the present invention.
Claims (6)
1. an activated coating that embeds ruthenium zirconium tin titanium oxide, is characterized in that: described activated coating is take iridium tantalum pentoxide as main body, has wherein embedded ruthenium zirconium tin titanium oxide.
2. the activated coating of embedding ruthenium zirconium tin titanium oxide according to claim 1, is characterized in that: the Ru:Zr:Sn:Ti mol ratio of described ruthenium zirconium tin titanium oxide is 3:1:3:3.
3. the activated coating of embedding ruthenium zirconium tin titanium oxide according to claim 1, is characterized in that: the Ir:Ta mol ratio of described iridium tantalum pentoxide is 65:35.
4. the activated coating of embedding ruthenium zirconium tin titanium oxide according to claim 1, is characterized in that: in described activated coating, Ru:Ir mol ratio is 25:75.
5. the activated coating of embedding ruthenium zirconium tin titanium oxide according to claim 1, is characterized in that: the particle diameter of described ruthenium zirconium tin titanium oxide is less than 10 nm.
6. a method of preparing the activated coating of embedding ruthenium zirconium tin titanium oxide as claimed in claim 1, is characterized in that: comprise the following steps:
(1) preparation of ruthenium zirconium tin titanium oxide active slurry: with RuCl
3, ZrCl
4, SnCl
4and TiCl
3for source material, be that 3:1:3:3 takes each source material by Ru:Zr:Sn:Ti mol ratio, and be dissolved in respectively butanols, after each source material fully dissolves, they are mixed, obtain ruthenium zirconium tin titanium oxide active slurry;
(2) sintering of ruthenium zirconium tin titanium oxide nanoparticles: extract ruthenium zirconium tin titanium oxide active slurry, after 90 ℃ are heating and curing, take out and grind, then oxidation and sinter in the box-type furnace of 380 ℃, come out of the stove cooling, after grinding, obtain ruthenium zirconium tin titanium oxide nanoparticles;
(3) preparation of iridium tantalum pentoxide active slurry: with H
2irCl
6and TaCl
5for source material, by Ir: Ta mol ratio takes each source material at 65: 35, and is dissolved in respectively butanols, after each source material fully dissolves, the two is mixed, and obtains iridium tantalum pentoxide active slurry;
(4) preparation of activated coating: mole total amount of pressing active substance, take 25% ruthenium zirconium tin titanium oxide nanoparticles and 75% iridium tantalum pentoxide active slurry, ruthenium zirconium tin titanium oxide nanoparticles is sneaked in iridium tantalum pentoxide active slurry, fully stir, be coated on the titanium base material of etching, after 110 ℃ are heating and curing, oxidation and sinter 10 minutes in the box-type furnace of 520 ℃, after cooling, row applies again, thermal treatment, come out of the stove cooling, repeat altogether 15 times, finally 520 ℃ of annealing 1 hour, obtain the iridium tantalum pentoxide active coated Ti that embeds ruthenium zirconium tin titanium oxide.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410037157.1A CN103774175B (en) | 2014-01-26 | 2014-01-26 | A kind ofly embed activated coating of ruthenium zirconium tin titanium oxide and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410037157.1A CN103774175B (en) | 2014-01-26 | 2014-01-26 | A kind ofly embed activated coating of ruthenium zirconium tin titanium oxide and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103774175A true CN103774175A (en) | 2014-05-07 |
| CN103774175B CN103774175B (en) | 2015-12-02 |
Family
ID=50566912
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410037157.1A Expired - Fee Related CN103774175B (en) | 2014-01-26 | 2014-01-26 | A kind ofly embed activated coating of ruthenium zirconium tin titanium oxide and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103774175B (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108048870A (en) * | 2017-12-20 | 2018-05-18 | 福州大学 | A kind of Ni-based active electrode material of embedded ruthenium Si composite oxide and preparation method thereof |
| CN108048869A (en) * | 2017-12-20 | 2018-05-18 | 福州大学 | A kind of Ni-based active electrode material of embedded ruthenium hafnium composite oxides and preparation method thereof |
| CN108048895A (en) * | 2017-12-20 | 2018-05-18 | 福州大学 | A kind of Ni-based active electrode material of embedded ruthenium zirconium mixed oxide 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 |
| CN112010400A (en) * | 2020-07-20 | 2020-12-01 | 西安怡速安智能科技有限公司 | Anode layer formula of electrochemical electrode for water sterilization |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN87103801A (en) * | 1986-05-22 | 1987-12-09 | 耐用电极株式会社 | Durable electrolytic electrode and manufacture method thereof |
| CN1052708A (en) * | 1989-12-22 | 1991-07-03 | Tdk株式会社 | Oxygen-generating electrode and preparation method thereof |
| CN1656254A (en) * | 2002-05-24 | 2005-08-17 | 德·诺拉电极股份公司 | Electrode for gas evolution and method for its production |
| CN102465312A (en) * | 2010-10-28 | 2012-05-23 | 拜尔材料科学股份公司 | Electrode for electrolytic chlorine production |
-
2014
- 2014-01-26 CN CN201410037157.1A patent/CN103774175B/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN87103801A (en) * | 1986-05-22 | 1987-12-09 | 耐用电极株式会社 | Durable electrolytic electrode and manufacture method thereof |
| CN1052708A (en) * | 1989-12-22 | 1991-07-03 | Tdk株式会社 | Oxygen-generating electrode and preparation method thereof |
| CN1656254A (en) * | 2002-05-24 | 2005-08-17 | 德·诺拉电极股份公司 | Electrode for gas evolution and method for its production |
| CN102465312A (en) * | 2010-10-28 | 2012-05-23 | 拜尔材料科学股份公司 | Electrode for electrolytic chlorine production |
Non-Patent Citations (2)
| Title |
|---|
| TENG ZHANG，ETC: "Phase structure and Microstructure of a Nanoscale TiO2-Ru02-IrO2-Ta2O5 Anode coating on Titanium", 《THE AMERICAN CERAMIC SOCIETY》 * |
| 潘懋: "钌钛金属阳极涂层改进的途径探讨", 《氯碱工业》 * |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108048870A (en) * | 2017-12-20 | 2018-05-18 | 福州大学 | A kind of Ni-based active electrode material of embedded ruthenium Si composite oxide and preparation method thereof |
| CN108048869A (en) * | 2017-12-20 | 2018-05-18 | 福州大学 | A kind of Ni-based active electrode material of embedded ruthenium hafnium composite oxides and preparation method thereof |
| CN108048895A (en) * | 2017-12-20 | 2018-05-18 | 福州大学 | A kind of Ni-based active electrode material of embedded ruthenium zirconium mixed oxide and preparation method thereof |
| CN108048895B (en) * | 2017-12-20 | 2019-12-17 | 福州大学 | nickel-based active electrode material embedded with ruthenium-zirconium composite oxide and preparation method thereof |
| CN108048870B (en) * | 2017-12-20 | 2019-12-17 | 福州大学 | Nickel-based active electrode material embedded with ruthenium-silicon composite oxide 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 |
| CN112010400A (en) * | 2020-07-20 | 2020-12-01 | 西安怡速安智能科技有限公司 | Anode layer formula of electrochemical electrode for water sterilization |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103774175B (en) | 2015-12-02 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103741165A (en) | Active coating layer embedded in ruthenium-titanium oxide and preparation method of active coating layer | |
| Wu et al. | Nano-crystalline RuxSn1− xO2 powder catalysts for oxygen evolution reaction in proton exchange membrane water electrolysers | |
| CN103774175B (en) | A kind ofly embed activated coating of ruthenium zirconium tin titanium oxide and preparation method thereof | |
| Huang et al. | Synthesis of high-performance titanium sub-oxides for electrochemical applications using combination of sol–gel and vacuum-carbothermic processes | |
| CN107034483B (en) | A kind of preparation method of hypochlorite generator's electrode | |
| Wang et al. | Hydrothermal synthesis of 3D hierarchically flower-like structure Ti/SnO2-Sb electrode with long service life and high electrocatalytic performance | |
| JP4804350B2 (en) | Electrode and method for producing the electrode | |
| Duan et al. | Novel composition graded Ti/Ru–Sb–SnO2 electrode synthesized by selective electrodeposition and its application for electrocatalytic decolorization of dyes | |
| Elsharkawya et al. | Electrodeposition of Ni nanoparticles from deep eutectic solvent and aqueous solution promoting high stability electrocatalyst for hydrogen and oxygen evolution reactions | |
| Wang et al. | Constructing of Pb–Sn/α-PbO2/β-PbO2-Co2MnO4 composite electrode for enhanced oxygen evolution and zinc electrowinning | |
| CN103305866B (en) | Preparation method of iridium oxide nanometer coating electrode taking aluminum oxide-based composite material as base body | |
| JPWO2019182088A1 (en) | Method for manufacturing low-order titanium oxide powder | |
| CN109546126A (en) | A kind of transition metal element doped carbon coating lithium titanate, preparation method and application | |
| CN102029152B (en) | Ru-Zr-Ti ternary oxide active material and preparation method thereof | |
| Silva et al. | Electronic structure, morphological aspects, optical and electrochemical properties of RuO 2 nanocrystals | |
| CN103774177B (en) | A kind ofly embed activated coating of ruthenium zirconium tin-oxide and preparation method thereof | |
| US9689080B2 (en) | Layered alkali iridate, layered iridic acid, and iridium oxide nanosheet | |
| CN101818361B (en) | Active material with high Zr proportioning and preparation method thereof | |
| Bacirhonde et al. | Reduction of transition-metal columbite-tantalite as a highly efficient electrocatalyst for water splitting | |
| Panić et al. | Electrocatalytic properties and stability of titanium anodes activated by the inorganic sol-gel procedure | |
| Wang et al. | Enhanced performance of a pillared TiO2 nanohybrid as an anode material for fast and reversible lithium storage | |
| CN102311264A (en) | Environment-protection and energy-saving nanometer zirconium oxide preparation method | |
| CN102220600B (en) | Iridium tantalum activating oxide having in situ embedded structure and preparation method thereof | |
| CN102225334B (en) | Active material containing Hf (hydrogen fluoride) oxide and preparation method thereof | |
| CN108706632B (en) | Preparation method of bismuth titanate nanosheet |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20151202 Termination date: 20210126 |