CN102251252A - Preparation method of seawater electrolytic reaction anode IrO2-RuO2-SnO2-TiO2 nanoparticle coating - Google Patents

Preparation method of seawater electrolytic reaction anode IrO2-RuO2-SnO2-TiO2 nanoparticle coating Download PDF

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CN102251252A
CN102251252A CN2011102030046A CN201110203004A CN102251252A CN 102251252 A CN102251252 A CN 102251252A CN 2011102030046 A CN2011102030046 A CN 2011102030046A CN 201110203004 A CN201110203004 A CN 201110203004A CN 102251252 A CN102251252 A CN 102251252A
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ruo
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陈煜�
梁燕
周益明
丁小余
唐亚文
陆天虹
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Nanjing Normal University
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Nanjing Normal University
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Abstract

The invention relates to a preparation method of a seawater electrolytic reaction anode IrO2-RuO2-SnO2-TiO2 nanoparticle coating. The seawater electrolytic reaction anode IrO2-RuO2-SnO2-TiO2 nanoparticle coating is prepared by the following improved thermal decomposition method: mixing soluble SnIV, RuIII and IrIV salt solution and titanium dioxide, adding high molecular polymer, and stirring or carrying out supersonic oscillation to form a suspension, thereby obtaining the anode coating liquid; and brushing the suspension on a Ti matrix, drying, calcining, cooling, and repeating many times until the coating reaches the required thickness. The anode coating prepared by the method provided by the invention has the advantages of uniform metallic oxide particle distribution, small microcrystal particle size, large specific area, increased electrode conductivity, excellent electrocatalytic activity and high stability, and has a mud crack appearance on the surface. The preparation method provided by the invention is simple, and suitable for industrial large-scale production.

Description

Seawater electrolysis reaction anode IrO＜sub〉2＜/sub 〉-RuO＜sub〉2＜/sub 〉-SnO＜sub〉2＜/sub 〉-TiO＜sub〉2＜/sub〉preparation method of nanoparticle coating
Technical field
The present invention relates to a kind of preparation method of anode coating of preparing chlorine by electrolysis reaction, be specifically related to a kind of anode IrO that utilizes improved thermolysis process to prepare the seawater electrolysis reaction 2-RuO 2-SnO 2-TiO 2The method of nanoparticle coating.
Background technology
Hypochlorite adopts DSA electrolysis saturated aqueous common salt to make as the important component of chlorine-containing disinfectant usually.The DSA electrode is regarded as one of most important invention in 20th century electrochemical field.The ruthenium titanium oxide coated electrode (Ti/RuTiO of refer initially to the mid-1960s Beer invention x), because of it has good electrochemical activity, anti-corrosion stability is called as dimensionally stable electrode (Dimensionally stable Anode is called for short DSA).In recent years, more and more scholars begins to pay close attention to electrolytic seawater and produces hypochlorite.Because do not need the additive decrementation chemical reagent when using seawater as electrolytic solution, saved cost greatly, thereby promote the application of the direct preparing chlorine by electrolysis method of seawater in power plant, factory, especially, have very important significance in the abundant coastland of seawater resources.
In the process of preparing chlorine by electrolysis, electrode is the focus of research always, because the activity of electrode and stability can directly influence whole electrolytic process.The main ingredient of DSA electrode is ruthenium dioxide and titanium dioxide.Must possess electroconductibility as electrode coating, titanium dioxide can not conduct electricity separately, has only titanium dioxide and ruthenium dioxide to form sosoloid, and such mixing just has electroconductibility.Ruthenium dioxide and titanium dioxide are easy to form the solid solution coating, and with the titanium dioxide solid solution again on titanium surface, make coating be bonded in the surface of titanium matrix securely, and the titanium matrix is highly stable in electrolytic solution, thereby has realized the industrialization of metal electrode.Ruthenium titanium oxide coated electrode at first is applied in chlorine industry, and has obtained howling success.But as the electrode that electrolytic seawater is used, the subject matter that the direct preparing chlorine by electrolysis technology of seawater exists has current efficiency low, and power consumption height and anode life are short etc.
Seawater electrolysis with the requirement of electrode than chlor-alkali much strict with electrode.In general, electrolytic seawater with metallic oxide coating electrode should have high chlorine oxygen selective can (low chloride potential and the high oxygen release current potential released), high current efficiency, fabulous erosion resistance, can be in bigger current density range and in the wide temperature range efficiently, stably work.Chinese scholars has been done big quantity research at these problems.These researchs mainly are the performances of setting about improving metallic oxide coating electrode from coating formula and preparation technology two aspects.Seawater electrolysis generally adopts the multi-element metal oxide coated electrode at present, contains other metal oxide containing precious metals such as Pt in the coating.These precious metals have good reaction selectivity, and corrosion strength is strong, are difficult for the characteristics of passivation, but its active ingredient price is very expensive, and expensive its development in future that will make is restricted to a certain extent.
At present, industrial titanium anode still mainly adopts thermal decomposition method preparation, this method very easily to cause defectives such as titanium anode coating structure organization, composition profiles inequality, degree of oxidation be uncertain.Therefore, searching can obtain the preparation method of high dispersing, highly uniform titanium anode coating, has become exploitation high-performance titanium anodic direction.
Summary of the invention
The purpose of this invention is to provide a kind of seawater electrolysis reaction anode IrO 2-RuO 2-SnO 2-TiO 2The preparation method of nanoparticle coating, in order to control the crystal particle scale of prepared anode coating effectively, prepare composite oxides by adding high molecular polymer improvement thermal decomposition method technology, moreover, obtain the microcrystal grain that the coating structure of nanostructure has small particle size by this method, show excellent electro catalytic activity and stability.
The technical scheme of finishing the foregoing invention task is:
A kind of seawater electrolysis reaction anode IrO 2-RuO 2-SnO 2-TiO 2The preparation method of nanoparticle coating is characterized in that: with solubility Sn IV, Ru IIIAnd Ir IVThe aqueous solution of salt and titanium dioxide mix, and add high molecular polymer, stir or sonic oscillation formation suspension liquid, make the anode electrode masking liquid; Then suspension liquid is brushed on the Ti matrix, the calcining of dry back, cooling is carried out repeatedly repeatedly, reaches needed thickness until coating, promptly makes described anode nanometer particle coating.
The preparation method of described mixed metal oxide nanoparticle anode coating is improved thermal decomposition method.When preparation anode electrode masking liquid, add high molecular polymer, with solubility Sn IV, Ru III, Ir IVThe aqueous solution of salt and titanium dioxide mix the formation suspension liquid, make the anode electrode masking liquid, then the electrode masking liquid are brushed and high-temperature calcination.Add high molecular polymer in the electrode masking liquid, can control the crystal particle scale of anode coating effectively, obtain the coating of the mixed metal oxide nanostructure of nominal particle size, dispersion homogeneous after the roasting.
More optimize and more particularly anode IrO of the present invention 2-RuO 2-SnO 2-TiO 2The preparation method of nanoparticle coating may further comprise the steps:
1) electrode masking liquid preparation: with solubility Sn IV, Ru III, Ir IVThe aqueous solution of salt and titanium dioxide mix, and add high molecular polymer, stir or sonic oscillation formation suspension liquid, make the anode electrode masking liquid;
2) mixed metal oxide nanoparticle preparation: the suspension liquid that step 1) makes is brushed on the Ti matrix drying, calcining, cooling;
3) coating preparation: repeat step 2), reach needed thickness until coating.
Described Sn IV, Ru IIIAnd Ir IVThe preferred SnCl of salt 4, RuCl 3And H 2IrCl 4, or their hydrate.
Described Sn IV, Ru III, Ir IVIn salt and the titanium dioxide, by mole per-cent, preferred Ir IVBe 5～20%, Ru IIIBe 30～50%, Sn IVBe 10～30%, TiO 2Be 5～25%; Ir most preferably IVAccount for 18.9%, Ru IIIAccount for 30.7%, Sn IVAccount for 29.2%, TiO 2Account for 21.2%.
Described titania support is selected from one or more in titanium dioxide nano-particle (rutile-type, Detitanium-ore-type), titania nanotube, the titanium dioxide nanofiber etc.
In the electrode masking liquid, described high molecular polymer is 0.001-0.002 g/ml.
Described high molecular polymer comprises polyvinyl alcohol, polyisobutene, polyacrylamide, polyoxyethylene glycol, polyvinylpyrrolidone, Polymethacrylimide etc., optimization polypropylene acid amides, polyoxyethylene glycol, one or more in the polyvinylpyrrolidone etc.Wherein polyacrylamide is a high molecular weight water soluble polymer, can reduce the frictional resistance between the liquid, and molecular weight is 4000～18000000, most preferably 3000000.Polyoxyethylene glycol has good water-solubility, and with many organic matter components good intermiscibility is arranged, and they have excellent lubrication, moisture retention, dispersiveness, and molecular weight is 2000～7500, and most preferably 6000.Polyvinylpyrrolidone has the general aspects of water-soluble high-molecular compound as a kind of synthesizing water-solubility macromolecular compound, has colloid provide protection, film-forming properties, cohesiveness, and molecular weight is 5000～700000, and most preferably 30000.These macromolecular compound aqueous solution generally have the high viscosity characteristic, all can effectively suppress the reunion of catalyst nanoparticles.
Described titanium matrix can carry out pre-treatment before brushing, purpose is in order to strengthen the bonding force of titanium matrix and coating of metal oxides, thereby improves electroconductibility, prolongs its work-ing life.Pre-treatment comprises oil removing, acid etching rust cleaning, sandblast or organic solution immersion treatment.
Described calcining temperature is preferably 500～600 ℃.
Described anode IrO 2-RuO 2-SnO 2-TiO 2The preferred Ti matrix weightening finish of its thickness of nanoparticle coating carrying capacity reaches 1.2-1.5 mg/cm 2
Utilize methods such as XRD, SEM, cyclic voltammetry curve that structure, pattern and the electro catalytic activity of prepared anode nanometer particle coating are characterized, experiment shows, according to the anode IrO of method for preparing 2-RuO 2-SnO 2-TiO 2Nanoparticle coating, the microcrystal grain with 10-30 nm small particle size, metal oxide nanoparticles is dispersed in titanium dioxide surface, metal oxide particle has favorable uniformity and dispersity, the surface has " mud crack " shape pattern, and uneven, coating has big specific surface area.Electrode conductivuty increases, and has excellent electro catalytic activity and stability.
The present invention utilizes improved thermal decomposition method to prepare the anode IrO of seawater electrolysis reaction 2-RuO 2-SnO 2-TiO 2Nanoparticle coating by adding high molecular polymer, can effectively be controlled grain-size, obtains the coating of the mixed metal oxide nanostructure of nominal particle size, dispersion homogeneous after the roasting.The IrO of the inventive method preparation 2-RuO 2-SnO 2-TiO 2Nanoparticle coating has the microcrystal grain of small particle size, shows excellent electro catalytic activity and stability.The improved thermolysis preparation method of the present invention is simple, is fit to the large-scale production of industry.
Describe the present invention below in conjunction with specific embodiment.Protection scope of the present invention is not exceeded with embodiment, but is limited by claim.
 
Description of drawings
Fig. 1: improve thermal decomposition method and make IrO 2-RuO 2-SnO 2-TiO 2The X-ray diffraction of coating (XRD).
Fig. 2: improve thermal decomposition method and make IrO 2-RuO 2-SnO 2-TiO 2The SEM photo of coating.
Fig. 3: the cyclic voltammogram of anode nanometer particle coating in 3.5%NaCl solution that the seawater electrolysis that utilizes the improvement thermal decomposition method to make reacts; Scanning speed: 20mV/s, temperature: 30 ℃.
Fig. 4: the polarization curve of anode nanometer particle coating in 3.5%NaCl solution that the seawater electrolysis that utilizes the improvement thermal decomposition method to make reacts; Scanning speed: 5mV/s, temperature: 30 ℃.
 
Embodiment
Embodiment 1
The IrO of seawater electrolysis reaction 2-RuO 2-SnO 2-TiO 2The anode nanometer particle coating by improving the thermal decomposition method preparation, may further comprise the steps:
1, takes by weighing titanium dioxide nano-particle 30mg, add 0.18g SnCl 45H 2O, 8ml 0.067mol/L RuCl 32H 2O, 5ml 0.067mol/L H 2IrCl 46H 2O solution adds molecular weight and is 3000000 polyacrylamide 0.001 g/ml subsequently, stirs or sonic oscillation, and it is mixed, and forms suspension liquid, makes the anode electrode masking liquid;
2, the suspension liquid that step 1) is made is brushed on the Ti sheet, 120 ℃ of dryings, 500 ℃ of high-temperature calcinations, cooling;
3, repeat step 2) about 20 times, reach 1.2mg/cm until Ti sheet weightening finish carrying capacity 2, promptly make described anode IrO 2-RuO 2-SnO 2-TiO 2Nanoparticle coating.
Embodiment 2
The IrO of seawater electrolysis reaction 2-RuO 2-SnO 2-TiO 2The anode nanometer particle coating improves the thermal decomposition method preparation, may further comprise the steps:
1, takes by weighing titania nanotube 30mg, add 0.15gSnCl 45H 2O, 8ml0.067mol/L RuCl 32H 2O, 6ml 0.067mol/L H 2IrCl 46H 2O solution adds molecular weight and is 3000000 polyacrylamide 0.0015g/ml subsequently, stirs or sonic oscillation, and it is mixed, and forms suspension liquid, promptly makes the anode electrode masking liquid;
2, the suspension liquid that step 1) is made is brushed on the Ti sheet, 120 ℃ of dryings, 500 ℃ of high-temperature calcinations, cooling;
3, repeat step 2) about 20 times, reach 1.4 mg/cm until Ti sheet weightening finish carrying capacity 2, promptly make described anode IrO 2-RuO 2-SnO 2-TiO 2Nanoparticle coating.
Embodiment 3
The IrO of seawater electrolysis reaction 2-RuO 2-SnO 2-TiO 2The anode nanometer particle coating improves the thermal decomposition method preparation, may further comprise the steps:
1, takes by weighing titanium dioxide nanofiber 30mg, add 0.18g SnCl 45H 2O, 8ml 0.067mol/L RuCl 32H 2O, 5ml 0.067mol/L H 2IrCl 46H 2O solution, adding molecular weight subsequently is 10000000 polyacrylamides, 0.002 g/ml, stirs or sonic oscillation, and it is mixed, and forms suspension liquid, promptly makes the anode electrode masking liquid;
2, the suspension liquid that step 1) is made is brushed on the Ti sheet, 120 ℃ of dryings, 600 ℃ of high-temperature calcinations, cooling;
3, carry out step 2 repeatedly) about 20 times, reach 1.5mg/cm until Ti sheet weightening finish carrying capacity 2, promptly make described anode IrO 2-RuO 2-SnO 2-TiO 2Nanoparticle coating.
Embodiment 4
The IrO of seawater electrolysis reaction 2-RuO 2-SnO 2-TiO 2The anode nanometer particle coating improves the thermal decomposition method preparation, may further comprise the steps:
1, takes by weighing titanium dioxide nano-particle 30mg, add 0.18g SnCl 45H 2O, 8ml 0.067mol/L RuCl 32H 2O, 5ml 0.067mol/L H 2IrCl 46H 2O solution adds molecular weight and is 6000 polyoxyethylene glycol 0.001 g/ml subsequently, stirs or sonic oscillation, and it is mixed, and forms suspension liquid, promptly makes the anode electrode masking liquid;
2, the suspension liquid that step 1) is made is brushed on the Ti sheet, 120 ℃ of dryings, 500 ℃ of high-temperature calcinations, cooling;
3, carry out step 2 repeatedly) about 20 times, reach 1.3 mg/cm until Ti sheet weightening finish carrying capacity 2, promptly make described anode IrO 2-RuO 2-SnO 2-TiO 2Nanoparticle coating.
Embodiment 5
The IrO of seawater electrolysis reaction 2-RuO 2-SnO 2-TiO 2The anode nanometer particle coating improves the thermal decomposition method preparation, may further comprise the steps:
1, takes by weighing titania nanotube 10mg, add 0.1g SnCl 45H 2O, 7.5ml 0.067mol/L RuCl 32H 2O, 0.75ml 0.067mol/L H 2IrCl 46H 2O solution adds molecular weight and is 7500 polyoxyethylene glycol 0.002 g/ml subsequently, stirs or sonic oscillation, and it is mixed, and forms suspension liquid, promptly makes the anode electrode masking liquid;
2, the suspension liquid that step 1) is made is brushed on the Ti sheet, drying, 500 ℃ of high-temperature calcinations, cooling;
3, repeat step 2) about about 20 times, reach 1.5 mg/cm until Ti sheet weightening finish carrying capacity 2, promptly make described anode IrO 2-RuO 2-SnO 2-TiO 2Nanoparticle coating.
Embodiment 6
The IrO of seawater electrolysis reaction 2-RuO 2-SnO 2-TiO 2The anode nanometer particle coating improves the thermal decomposition method preparation, may further comprise the steps:
1, takes by weighing titanium dioxide nanofiber 30mg, add 0.18g SnCl 45H 2O, 8ml 0.067mol/L RuCl 32H 2O, 5ml 0.067mol/L H 2IrCl 46H 2O solution adds molecular weight and is 6000 polyoxyethylene glycol 0.001g/ml subsequently, stirs or sonic oscillation, and it is mixed, and forms suspension liquid, promptly makes the anode electrode masking liquid;
2, the suspension liquid that step 1) is made is brushed on the Ti sheet, drying, 500 ℃ of high-temperature calcinations, cooling;
3, repeat step 2) about about 20 times, reach 1.5 mg/cm until Ti sheet weightening finish carrying capacity 2, promptly make described anode IrO 2-RuO 2-SnO 2-TiO 2Nanoparticle coating.
Embodiment 7
The IrO of seawater electrolysis reaction 2-RuO 2-SnO 2-TiO 2The anode nanometer particle coating improves the thermal decomposition method preparation, may further comprise the steps:
1, takes by weighing titanium dioxide nano-particle 16mg, add 0.1g SnCl 45H 2O, 4.5ml 0.067mol/L RuCl 32H 2O, 3ml 0.067mol/L H 2IrCl 46H 2O solution adds molecular weight and is 30000 polyvinylpyrrolidone 0.001 g/ml subsequently, stirs or sonic oscillation, and it is mixed, and forms suspension liquid, promptly makes the anode electrode masking liquid;
2, the suspension liquid that step 1) is made is brushed on the Ti sheet, drying, 600 ℃ of high-temperature calcinations, cooling;
3, repeat step 2) about about 20 times, reach 1.2 mg/cm until Ti sheet weightening finish carrying capacity 2, promptly make described anode IrO 2-RuO 2-SnO 2-TiO 2Nanoparticle coating.
Embodiment 8
The IrO of seawater electrolysis reaction 2-RuO 2-SnO 2-TiO 2The anode nanometer particle coating improves the thermal decomposition method preparation, may further comprise the steps:
1, takes by weighing synthetic titania nanotube 30mg, add 0.18gSnCl 45H 2O, 8ml0.067mol/L RuCl 32H 2O, 5ml 0.067mol/L H 2IrCl 46H 2O solution adds molecular weight and is 50000 polyvinylpyrrolidone 0.002 g/ml subsequently, stirs or sonic oscillation, and it is mixed, and forms suspension liquid, promptly makes the anode electrode masking liquid;
2, the suspension liquid that step 1) is made is brushed on the Ti sheet, drying, 600 ℃ of high-temperature calcinations, cooling;
3, repeat step 2) about about 20 times, reach 1.3 mg/cm until Ti sheet weightening finish carrying capacity 2, promptly make described anode IrO 2-RuO 2-SnO 2-TiO 2Nanoparticle coating.
Embodiment 9
The IrO of seawater electrolysis reaction 2-RuO 2-SnO 2-TiO 2The anode nanometer particle coating improves the thermal decomposition method preparation, may further comprise the steps:
1, takes by weighing synthetic titanium dioxide nanofiber 30mg, add 0.18g SnCl 45H 2O, 8ml 0.067mol/L RuCl 32H 2O, 5ml 0.067mol/L H 2IrCl 46H 2O solution adds molecular weight and is 30000 polyvinylpyrrolidone 0.001 g/ml subsequently, stirs or sonic oscillation, and it is mixed, and forms suspension liquid, promptly makes the anode electrode masking liquid;
2, the suspension liquid that step 1) is made is brushed on the Ti sheet, drying, 500 ℃ of high-temperature calcinations, cooling;
3, repeat step 2) about about 20 times, reach 1.5 mg/cm until Ti sheet weightening finish carrying capacity 2, promptly make described anode IrO 2-RuO 2-SnO 2-TiO 2Nanoparticle coating.
Embodiment 10
The IrO of seawater electrolysis reaction 2-RuO 2-SnO 2-TiO 2The anode nanometer particle coating improves the thermal decomposition method preparation, may further comprise the steps:
1, takes by weighing synthetic titanium dioxide nanofiber 20mg, add 0.05g SnCl 45H 2O, 7ml 0.067mol/L RuCl 32H 2O, 3ml 0.067mol/L H 2IrCl 46H 2O solution adds molecular weight and is 30000 polyvinylpyrrolidone 0.002 g/ml subsequently, stirs or sonic oscillation, and it is mixed, and forms suspension liquid, promptly makes the anode electrode masking liquid;
2, the suspension liquid that step 1) is made is brushed on the Ti sheet, drying, 500 ℃ of high-temperature calcinations, cooling;
3, repeat step 2) about about 20 times, reach 1.5 mg/cm until Ti sheet weightening finish carrying capacity 2, promptly make described anode IrO 2-RuO 2-SnO 2-TiO 2Nanoparticle coating.
Fig. 1 is IrO 2-RuO 2-SnO 2-TiO 2The X-ray diffraction of coating (XRD) collection of illustrative plates.
Fig. 2 is IrO 2-RuO 2-SnO 2-TiO 2The SEM photo of coating.Photo clearly demonstrates the anode coating metal oxide nanoparticles that improved thermal decomposition method makes and is dispersed in titanium dioxide surface, metal oxide particle has favorable uniformity and dispersity, the surface has " mud crack " shape pattern, uneven, therefore coating has big specific surface area, make the electro catalytic activity of electrode raise the anode conducting increase.
Fig. 3 is IrO 2-RuO 2-SnO 2-TiO 2The cyclic voltammogram of coating in 3.5%NaCl solution.Area that the cyclic voltammetry curve of electrode surrounded has reflected that electrode participates in what of volt-ampere electric charge of chemical reaction, and cyclic voltammetric electric weight q is directly proportional with the surfactivity number of spots, therefore, can adopt the integral charge amount q on the cyclic voltammetry curve that records in the certain potentials scope, describe the active surface area of coated anode, and then reflect the overall activity of anode coating.Fig. 3 has shown IrO 2-RuO 2-SnO 2-TiO 2Coated anode has bigger active surface area, and electro catalytic activity is better, this main and IrO 2-RuO 2-SnO 2-TiO 2The high-specific surface area that coating has also has defect structure relevant.
Fig. 4 is IrO 2-RuO 2-SnO 2-TiO 2The polarization curve of coating in 3.5%NaCl solution, as can be seen from the figure, IrO 2-RuO 2-SnO 2-TiO 2Coated anode has less polarizability, therefore has more superior electrocatalysis characteristic.

Claims (12)

1. a seawater electrolysis reacts anode IrO 2-RuO 2-SnO 2-TiO 2The preparation method of nanoparticle coating is characterized in that: with solubility Sn IV, Ru IIIAnd Ir IVThe aqueous solution of salt and titanium dioxide mix, and add high molecular polymer, stir or sonic oscillation formation suspension liquid, make the anode electrode masking liquid; Then suspension liquid is brushed on the Ti matrix, the calcining of dry back, cooling is carried out repeatedly repeatedly, reaches needed thickness until coating, promptly makes described anode nanometer particle coating.
2. anode IrO according to claim 1 2-RuO 2-SnO 2-TiO 2The preparation method of nanoparticle coating is characterized in that, described method may further comprise the steps:
1) electrode masking liquid preparation: with solubility Sn IV, Ru III, Ir IVThe aqueous solution of salt and titanium dioxide mix, and add high molecular polymer, stir or sonic oscillation formation suspension liquid, make the anode electrode masking liquid;
2) mixed metal oxide nanoparticle preparation: the suspension liquid that step 1) makes is brushed on the Ti matrix drying, calcining, cooling;
3) coating preparation: repeat step 2), reach needed thickness until coating.
3. anode IrO according to claim 1 and 2 2-RuO 2-SnO 2-TiO 2The preparation method of nanoparticle coating is characterized in that: described Sn IV, Ru IIIAnd Ir IVSalt is SnCl 4, RuCl 3And H 2IrCl 4, or their hydrate.
4. anode IrO according to claim 1 and 2 2-RuO 2-SnO 2-TiO 2The preparation method of nanoparticle coating is characterized in that: described Sn IV, Ru III, Ir IVIn salt and the titanium dioxide, by mole per-cent, Ir IVBe 5～20%, Ru IIIBe 30～50%, Sn IVBe 10～30%, TiO 2Be 5～25%.
5. anode IrO according to claim 1 and 2 2-RuO 2-SnO 2-TiO 2The preparation method of nanoparticle coating is characterized in that: described titania support is selected from rutile or anatase titanium dioxide nanoparticle, titania nanotube, one or more in the titanium dioxide nanofiber.
6. anode IrO according to claim 1 and 2 2-RuO 2-SnO 2-TiO 2The preparation method of nanoparticle coating is characterized in that: in the electrode masking liquid, described high molecular polymer is 0.001-0.002 g/ml.
7. anode IrO according to claim 1 and 2 2-RuO 2-SnO 2-TiO 2The preparation method of nanoparticle coating is characterized in that, described high molecular polymer is selected from polyacrylamide, polyoxyethylene glycol, polyvinylpyrrolidone, polyvinyl alcohol, polyisobutene, one or more in the Polymethacrylimide.
8. anode IrO according to claim 7 2-RuO 2-SnO 2-TiO 2The preparation method of nanoparticle coating is characterized in that, described high molecular polymer is that molecular weight is 4000～18000000 polyacrylamide, is that 2000～7500 molecular weight polyethylene glycol or molecular weight are 5000～700000 polyvinylpyrrolidone.
9. anode IrO according to claim 1 and 2 2-RuO 2-SnO 2-TiO 2The preparation method of nanoparticle coating is characterized in that, described calcining temperature is 500～600 ℃.
10. anode IrO according to claim 1 and 2 2-RuO 2-SnO 2-TiO 2The preparation method of nanoparticle coating is characterized in that, described anode IrO 2-RuO 2-SnO 2-TiO 2Its thickness of nanoparticle coating reaches 1.2-1.5 mg/cm for Ti matrix weightening finish carrying capacity 2
11. anode IrO according to claim 1 and 2 2-RuO 2-SnO 2-TiO 2The preparation method of nanoparticle coating is characterized in that, the particle diameter of described nanoparticle coating microcrystal grain is 10-30 nm.
12. anode IrO according to claim 1 and 2 2-RuO 2-SnO 2-TiO 2The preparation method of nanoparticle coating is characterized in that, described nanoparticle coating surface has " mud crack " shape pattern.
CN2011102030046A 2011-07-20 2011-07-20 Preparation method of seawater electrolytic reaction anode IrO2-RuO2-SnO2-TiO2 nanoparticle coating Pending CN102251252A (en)

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CN106011918A (en) * 2016-07-11 2016-10-12 青岛双瑞海洋环境工程股份有限公司 Seawater-electrolysis chlorine producing electrolytic bath used for resisting manganese pollution
CN109906287A (en) * 2016-10-28 2019-06-18 巴斯夫欧洲公司 Electrocatalyst composition comprising the metal oxide containing precious metals being supported on tin oxide
CN109906287B (en) * 2016-10-28 2022-06-21 巴斯夫欧洲公司 Electrocatalyst compositions comprising noble metal oxides supported on tin oxide
CN112368073A (en) * 2018-06-12 2021-02-12 国立研究开发法人科学技术振兴机构 Catalyst and method of use thereof
CN112368073B (en) * 2018-06-12 2024-04-09 国立研究开发法人科学技术振兴机构 Catalyst and method of use thereof
US11965255B2 (en) 2018-06-12 2024-04-23 Japan Science And Technology Agency Catalyst and method of use thereof
CN110983366A (en) * 2019-12-30 2020-04-10 中国科学院过程工程研究所 Electrocatalytic coating composition, dimensionally stable anode, preparation method and application

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