CN103774175B - A kind ofly embed activated coating of ruthenium zirconium tin titanium oxide and preparation method thereof - Google Patents
A kind ofly embed activated coating of ruthenium zirconium tin titanium oxide and preparation method thereof Download PDFInfo
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- CN103774175B CN103774175B CN201410037157.1A CN201410037157A CN103774175B CN 103774175 B CN103774175 B CN 103774175B CN 201410037157 A CN201410037157 A CN 201410037157A CN 103774175 B CN103774175 B CN 103774175B
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- titanium oxide
- zirconium tin
- tin titanium
- ruthenium zirconium
- ruthenium
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Abstract
The invention discloses and a kind ofly embed activated coating of ruthenium zirconium tin titanium oxide and preparation method thereof, described activated coating is based on iridium tantalum pentoxide, which is embedded ruthenium zirconium tin titanium oxide.Controlling to obtain yardstick by sintering temperature is the nanometer ruthenium zirconium tin titanium oxide powder being about less than 10nm.Nanometer ruthenium zirconium tin titanium oxide powder is mixed in iridium tantalum pentoxide presoma, after being heating and curing, in the box-type furnace of 520 DEG C oxidation and sinter and annealing after, Embedded iridium tantalum pentoxide activated coating can be obtained.Active material of the present invention has concurrently analyses oxygen and analyses chlorine performance, considerably improves iridium tantalum active oxide coatings synthetic activity, and has stronger practicality.Preparation method of the present invention has simple and convenient, workable, the feature that cost performance is high.
Description
Technical field
The invention belongs to the electrode materials field of Applied Electrochemistry and energy industry, relate to and a kind of there is material of high electrocatalysis characteristic and preparation method thereof.Concrete Application Areas comprises electrochemical component and the devices such as acid electrolytic solution, weak brine electrolysis, organic solution electrolysis, cathodic protection, electrochemical sensor.Be suitable for especially analysing in electrolyzer at chlorine, oxygen pair the activated coating being used as electrode materials.
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 kind of anode high analyse chlorine activity.Through large quantity research, in activated coating, with RuO
2+ TiO
2the binary oxide be composited has more superior over-all properties, is to analyse the industrial coated material the most generally adopted 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. propose the demand adopting iridium base oxide can realize 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, singlely traditionally analyses Cl
2, analyse O
2day by day highlight by the limitation of anode.In producing at electrometallurgy field, the electrolytic acid aqueous solution and perchlorate, more situation exists containing oxygen and chlorine-containing compound in electrolytic solution, and make electrolytic environments more harsh, therefore electrode materials is also subject to more acid test.For this reason, research and develop that oxygen, chlorine are two analyses electrode materials and have very important practical significance.In order to the activated coating of development of new, this research team is round TiO
2+ RuO
2and IrO
2+ Ta
2o
5conduct in-depth research, achieve certain achievement, as in 91 volumes of 2008 " American Ceramics association journal " with " PhaseStructureandMicrostructureofaNanoscaleTiO
2-RuO
2-IrO
2-Ta
2o
5anodeCoatingonTitanium " be 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 adopting the activity of alternating structure " to have the preparation method of the Ni―Ti anode of alternating structure coating ", obtain patent for invention.These coatings play obvious effect in the solidity to corrosion improving Ni―Ti anode.Recently, the research of this research group finds to adopt the method embedding ruthenium system oxide compound, more can realize the regulation and control of ruthenium system and iridium system active substance and performance.Namely at IrO
2-Ta
2o
5ruO is added in coating oxidation thing
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, the characteristic analysed oxygen simultaneously He analyse chlorine can be obtained, thus efficient oxygen can be obtained, chlorine is two analyses activated coating electrode materials.
Summary of the invention
The object of this invention is to provide and a kind ofly embed activated coating of ruthenium zirconium tin titanium oxide and preparation method thereof, thus obtain the high reactivity electrode materials having stronger pervasive effect.
Thinking of the present invention is in original iridium tantalum pentoxide activated coating, utilizes embedded technology in this coating, add ruthenium zirconium tin titanium oxide, can analyse oxygen at the same time to improve iridium tantalum pentoxide and analyse in chlorine occasion and have more superior activity.This thinking be based on iridium tantalum pentoxide and ruthenium titanium oxide be respectively generally acknowledge at present analyse chlorine and analyse two the most frequently used class active electrode materials of oxygen, 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, singlely traditionally analyses Cl
2, analyse O
2day by day highlight by the limitation of anode.In order to adapt to this change, this team proposes to adopt in iridium tantalum pentoxide activated coating, embeds ruthenium zirconium tin titanium oxide, make electrode under arms in process, except the oxygen evolution reaction of iridium tantalum pentoxide, the exposed ruthenium zirconium tin titanium oxide on surface can carry out analysing chlorine reaction, the effective active of the electrode of enhancing.This oxygen, chlorine pair are analysed electrode materials and are had very important practical significance.
Principle of operation of the present invention adds part nano level ruthenium zirconium tin titanium active oxidation composition granule exactly in iridium tantalum pentoxide presoma.We find in recent research, and the ruthenium zirconium tin titanium oxide of small scale obtains than the easier of ruthenium titanium oxide.Described damascene structures comes from the effect that the insert that adopts particle diameter to be about < 10nm adds, thus obtain and have the similar structure of matrix material.Again by ruthenium zirconium tin titanium oxide nanoscale and the ratio control with iridium tantalum pentoxide, what can obtain needs analyses oxygen and the performance analysing chlorine.Because the dosage of insert produces obviously impact to the internal organizational structure of active material, add very little, embed interface increasing amount limited, then the active limited efficiency improved.Add too many, the interface accounting of embedding is too high, affects the associativity of active material, has a negative impact to corrosion resisting property.Found by research, adopt tiny ruthenium zirconium tin titanium active oxidation composition granule, the content of insert can be made to improve.Therefore, the molar weight of insert active substance, when reaching the 25mol% being coated with stratum total, can have best over-all properties.
Prepared by employing embedding inlay technique of the present invention comprises with the core technology of the nanocrystalline iridium tantalum active oxide coatings for insert of ruthenium zirconium tin titanium oxide, and (1) first prepares ruthenium zirconium tin titanium oxide, and it has suitable nanoscale; (2) mix with the presoma of iridium tantalum activating oxide, common deposition is with on titanium base material; (3) thermal treatment of the iridium tantalum pentoxide coating containing 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) the sintering preparation of ruthenium zirconium tin titanium oxide nanoparticles: extract ruthenium zirconium tin titanium oxide active slurry, after being heating and curing, then oxidation and sinter, obtains the insert with the ruthenium zirconium tin titanium oxide of nanoscale.
(3) preparation of iridium tantalum pentoxide slurries: with H
2irCl
6and TaCl
5for source material, take each source material in proportion, the two is mixed, obtains active slurry;
(4) preparation of activated coating: ruthenium zirconium tin titanium oxide nanoparticles is mixed in iridium tantalum pentoxide active slurry, fully stirs, be coated on titanium base material; after being heating and curing; oxidation and sinter, finally anneals, and namely obtains the iridium tantalum pentoxide active coated Ti embedding ruthenium zirconium tin titanium oxide.
Remarkable advantage of the present invention is:
(1) the present invention effectively make use of the principle of the increase crystal boundary ratio of nanotechnology and matrix material, imports a large amount of damascene structures by embedding grammar.Add the number of channels of proton, thus the activity of electrode materials is improved.
(2) due to the nano-powder of the fine dimension by preparing the dispersion had in advance, the crystal miniaturization of final ruthenium zirconium tin titanium oxide is made after embedding, add the density in active centre, thus the actual bearer current density at electrode activity center is declined, thus the activity of electrode materials is improved.
(3) owing to adding part nano level ruthenium zirconium tin titanium active oxidation composition granule in iridium tantalum pentoxide presoma.Can pass through the ratio control of ruthenium zirconium tin titanium oxide and iridium tantalum pentoxide, what can obtain needs analyses oxygen and the performance analysing chlorine.Because coating of the present invention is based on iridium tantalum pentoxide, so the activity of its gassing mainly analyses oxygen, secondary is analyse chlorine.
(4) the present invention is solidified in advance owing to have employed traditional ruthenium zirconium tin titanium oxide active slurry, dispersion, the method for refinement, and making and the storage of raw material are all easy to.Added in iridium tantalum active slurry, electrode materials can be prepared by traditional technology.Therefore technique is simple, easy, does not totally make tooling cost increase.Owing to improving the performance of electrode materials, the cost performance of electrode product is made to 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 with the iridium tantalum pentoxide of 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 butanols respectively, concentration controls at about 0.3mol/L, they is mixed after each source material fully dissolves, and obtains ruthenium zirconium tin titanium oxide active slurry;
(2) the sintering preparation of ruthenium zirconium tin titanium oxide nanoparticles: quantitatively extract ruthenium zirconium tin titanium oxide active slurry, after being heating and curing through 90 DEG C, take out grinding, then oxidation and sinter in the box-type furnace of 380 DEG C, to come out of the stove cooling, after grinding, obtain the insert with the ruthenium zirconium tin titanium oxide of nanoscale.
(3) preparation of iridium tantalum pentoxide slurries: with H
2irCl
6and TaCl
5for source material, take each source material in the ratio of Ir: Ta mol ratio 65: 35, and be dissolved in butanols respectively, concentration controls at about 0.2mol/L, the two is mixed, obtain active slurry after each source material fully dissolves;
(4) preparation of activated coating: the iridium tantalum active slurry extracting ruthenium zirconium tin titanium oxide nano-powder and 75mol% by the 25mol% of mole total amount of active substance, ruthenium zirconium tin titanium oxide nanoparticles is mixed in iridium tantalum pentoxide active slurry, abundant stirring, be coated on the titanium base material after 10% oxalic acid that seethes with excitement etches 1 hour cleaning-drying, after being heating and curing through 110 DEG C, oxidation and sinter 10 minutes in the box-type furnace of 520 DEG C, row coating again after cooling, thermal treatment, to come out of the stove cooling, repeat 15 times altogether, finally 520 DEG C of annealing 1 hour, namely the iridium tantalum pentoxide active coated Ti embedding ruthenium zirconium tin titanium oxide is obtained.
The present invention obtains the iridium tantalum pentoxide active titanium anode that embedded in ruthenium zirconium tin titanium oxide nanostructure by above-mentioned enforcement.Research shows, the refinement of crystal grain and increasing of crystal boundary, effectively improves the active centre density of activating oxide, improves 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 embedding ruthenium zirconium tin titanium oxide structure, be provided with the activity analysed oxygen simultaneously He analyse chlorine.Carry out contrast experiment with the traditional iridium tantalum pentoxide active material prepared 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 for without embedded structure and have the iridium tantalum pentoxide active material of embedded structure analysing oxygen and analyse chlorine performance under parallel laboratory test condition.Can clearly find out, the Ni―Ti anode of embedded structure is suitable with the oxygen evolution potential of traditional Ni―Ti anode in the performance analysing oxygen, but its current potential of analysing chlorine obviously reduces.This fully shows, has that the iridium tantalum pentoxide active material embedding ruthenium zirconium tin titanium oxide nanostructure has good oxygen, chlorine is two analyses performance.
Below describe one embodiment of the present of invention in detail, but the present invention is not only limited to this.
Embodiment 1
The preparation adding the iridium tantalum activating oxide covering electrodes material of 25mol% insert is carried 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 being 3:1:3:3 in Ru:Zr:Sn:Ti mol ratio takes each source material, and is dissolved in butanols respectively, and concentration controls at 0.3mol/L, they is mixed after each source material fully dissolves, and obtains ruthenium zirconium tin titanium oxide active slurry;
(2) the sintering preparation of ruthenium zirconium tin titanium oxide nanoparticles: quantitatively extract ruthenium zirconium tin titanium oxide active slurry, after being heating and curing through 90 DEG C, take out grinding, then oxidation and sinter in the box-type furnace of 380 DEG C, to come out of the stove cooling, after grinding, obtain and there is the insert that nanoscale is the ruthenium zirconium tin titanium oxide of 8nm.
(3) preparation of iridium tantalum pentoxide slurries: with H
2irCl
6and TaCl
5for source material, take each source material in the ratio of Ir: Ta mol ratio 65: 35, and be dissolved in butanols respectively, concentration controls at 0.2mol/L, the two is mixed, obtain active slurry after each source material fully dissolves;
(4) preparation of activated coating: the iridium tantalum active slurry extracting ruthenium zirconium tin titanium oxide nano-powder and 75mol% by the 25mol% of mole total amount of active substance, ruthenium zirconium tin titanium oxide nanoparticles is mixed in iridium tantalum pentoxide active slurry, abundant stirring, be coated on the titanium base material of etching, after being heating and curing through 110 DEG C, oxidation and sinter 10 minutes in the box-type furnace of 520 DEG C, row coating again after cooling, thermal treatment, to come out of the stove cooling, repeat 15 times altogether, finally 520 DEG C of annealing 1 hour, namely the iridium tantalum pentoxide active coated Ti embedding ruthenium zirconium tin titanium oxide is obtained.
Table 1 has the electrochemical properties of the iridium tantalum pentoxide Ni―Ti anode embedding ruthenium zirconium tin titanium oxide structure
The foregoing is only preferred embodiment of the present invention, all equalizations done 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 (3)
1. embed an activated coating for ruthenium zirconium tin titanium oxide, it is characterized in that: described activated coating is based on iridium tantalum pentoxide, which is embedded ruthenium zirconium tin titanium oxide;
The Ru:Zr:Sn:Ti mol ratio of described ruthenium zirconium tin titanium oxide is 3:1:3:3;
In described activated coating, Ru:Ir mol ratio is 25:75;
The particle diameter of described ruthenium zirconium tin titanium oxide is less than 10nm.
2. 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.
3. prepare the method embedding the activated coating of ruthenium zirconium tin titanium oxide as claimed in claim 1, it 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 butanols respectively, 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 being heating and curing through 90 DEG C, take out grinding, then oxidation and sinter in the box-type furnace of 380 DEG C, to 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, take each source material by Ir: Ta mol ratio 65: 35, and be dissolved in butanols respectively, after each source material fully dissolves, the two is mixed, obtain iridium tantalum pentoxide active slurry;
(4) preparation of activated coating: by mole total amount of active substance, take 25% ruthenium zirconium tin titanium oxide nanoparticles and 75% iridium tantalum pentoxide active slurry, ruthenium zirconium tin titanium oxide nanoparticles is mixed in iridium tantalum pentoxide active slurry, abundant stirring, be coated on the titanium base material of etching, after being heating and curing through 110 DEG C, oxidation and sinter 10 minutes in the box-type furnace of 520 DEG C, row coating again after cooling, thermal treatment, to come out of the stove cooling, repeat 15 times altogether, finally 520 DEG C of annealing 1 hour, namely the iridium tantalum pentoxide active coated Ti embedding ruthenium zirconium tin titanium oxide is obtained.
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| CN108048869B (en) * | 2017-12-20 | 2019-08-09 | 福州大学 | A kind of Ni-based active electrode material and preparation method thereof being embedded in ruthenium hafnium composite oxides |
| 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 |
| 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 |
| 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 |
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