CN114395757A - Multi-oxide coating titanium anode plate and preparation method thereof - Google Patents
Multi-oxide coating titanium anode plate and preparation method thereof Download PDFInfo
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- CN114395757A CN114395757A CN202111457237.9A CN202111457237A CN114395757A CN 114395757 A CN114395757 A CN 114395757A CN 202111457237 A CN202111457237 A CN 202111457237A CN 114395757 A CN114395757 A CN 114395757A
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- oxide
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- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 title claims abstract description 100
- 229910052719 titanium Inorganic materials 0.000 title claims abstract description 100
- 239000010936 titanium Substances 0.000 title claims abstract description 100
- 239000011248 coating agent Substances 0.000 title claims abstract description 92
- 238000000576 coating method Methods 0.000 title claims abstract description 92
- 238000002360 preparation method Methods 0.000 title claims abstract description 34
- 239000000758 substrate Substances 0.000 claims abstract description 51
- 239000002904 solvent Substances 0.000 claims abstract description 23
- 239000002253 acid Substances 0.000 claims abstract description 21
- 239000004094 surface-active agent Substances 0.000 claims abstract description 13
- -1 iridium tantalum molybdenum samarium Chemical compound 0.000 claims abstract description 7
- 229910052751 metal Inorganic materials 0.000 claims description 50
- 239000002184 metal Substances 0.000 claims description 50
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 43
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 42
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 36
- 238000005245 sintering Methods 0.000 claims description 36
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 28
- 238000001035 drying Methods 0.000 claims description 24
- 238000010438 heat treatment Methods 0.000 claims description 21
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 20
- 238000009835 boiling Methods 0.000 claims description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 20
- HTXDPTMKBJXEOW-UHFFFAOYSA-N dioxoiridium Chemical compound O=[Ir]=O HTXDPTMKBJXEOW-UHFFFAOYSA-N 0.000 claims description 19
- FKTOIHSPIPYAPE-UHFFFAOYSA-N samarium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[Sm+3].[Sm+3] FKTOIHSPIPYAPE-UHFFFAOYSA-N 0.000 claims description 18
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 claims description 16
- 235000006408 oxalic acid Nutrition 0.000 claims description 14
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 14
- 238000003756 stirring Methods 0.000 claims description 13
- OEIMLTQPLAGXMX-UHFFFAOYSA-I tantalum(v) chloride Chemical compound Cl[Ta](Cl)(Cl)(Cl)Cl OEIMLTQPLAGXMX-UHFFFAOYSA-I 0.000 claims description 13
- 238000000137 annealing Methods 0.000 claims description 12
- 238000005530 etching Methods 0.000 claims description 12
- 239000007788 liquid Substances 0.000 claims description 12
- PBCFLUZVCVVTBY-UHFFFAOYSA-N tantalum pentoxide Inorganic materials O=[Ta](=O)O[Ta](=O)=O PBCFLUZVCVVTBY-UHFFFAOYSA-N 0.000 claims description 12
- 238000009210 therapy by ultrasound Methods 0.000 claims description 12
- 238000001816 cooling Methods 0.000 claims description 10
- 229910000457 iridium oxide Inorganic materials 0.000 claims description 10
- DHRLEVQXOMLTIM-UHFFFAOYSA-N phosphoric acid;trioxomolybdenum Chemical compound O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.OP(O)(O)=O DHRLEVQXOMLTIM-UHFFFAOYSA-N 0.000 claims description 10
- 229910001954 samarium oxide Inorganic materials 0.000 claims description 10
- 229940075630 samarium oxide Drugs 0.000 claims description 10
- 238000005488 sandblasting Methods 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 7
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 5
- 150000008052 alkyl sulfonates Chemical class 0.000 claims description 4
- 229940077388 benzenesulfonate Drugs 0.000 claims description 3
- 150000002148 esters Chemical class 0.000 claims description 3
- 229910052708 sodium Inorganic materials 0.000 claims description 3
- 239000011734 sodium Substances 0.000 claims description 3
- 239000003945 anionic surfactant Substances 0.000 claims description 2
- BPUBBGLMJRNUCC-UHFFFAOYSA-N oxygen(2-);tantalum(5+) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Ta+5].[Ta+5] BPUBBGLMJRNUCC-UHFFFAOYSA-N 0.000 claims description 2
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 claims description 2
- 239000000243 solution Substances 0.000 abstract description 47
- 230000000694 effects Effects 0.000 abstract description 15
- ULFQGKXWKFZMLH-UHFFFAOYSA-N iridium tantalum Chemical compound [Ta].[Ir] ULFQGKXWKFZMLH-UHFFFAOYSA-N 0.000 abstract description 13
- 229910052761 rare earth metal Inorganic materials 0.000 abstract description 9
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 8
- 239000001301 oxygen Substances 0.000 abstract description 8
- 229910052760 oxygen Inorganic materials 0.000 abstract description 8
- KZUNJOHGWZRPMI-UHFFFAOYSA-N samarium atom Chemical compound [Sm] KZUNJOHGWZRPMI-UHFFFAOYSA-N 0.000 abstract description 8
- 229910052772 Samarium Inorganic materials 0.000 abstract description 7
- 229910052723 transition metal Inorganic materials 0.000 abstract description 7
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 abstract description 6
- 239000011733 molybdenum Substances 0.000 abstract description 6
- 238000003980 solgel method Methods 0.000 abstract description 6
- 229910052750 molybdenum Inorganic materials 0.000 abstract description 5
- 239000008151 electrolyte solution Substances 0.000 abstract description 4
- 239000002243 precursor Substances 0.000 abstract description 3
- 150000003624 transition metals Chemical class 0.000 abstract description 3
- 239000003792 electrolyte Substances 0.000 abstract description 2
- 229910021645 metal ion Inorganic materials 0.000 abstract description 2
- 230000035515 penetration Effects 0.000 abstract description 2
- 239000000843 powder Substances 0.000 abstract description 2
- 230000002035 prolonged effect Effects 0.000 abstract description 2
- 239000006185 dispersion Substances 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 16
- 239000000203 mixture Substances 0.000 description 9
- 238000002484 cyclic voltammetry Methods 0.000 description 5
- 230000010287 polarization Effects 0.000 description 5
- 239000000084 colloidal system Substances 0.000 description 3
- VONLASUMRVUZLY-UHFFFAOYSA-N [Ir].[Ti].[Ta] Chemical compound [Ir].[Ti].[Ta] VONLASUMRVUZLY-UHFFFAOYSA-N 0.000 description 2
- 230000005518 electrochemistry Effects 0.000 description 2
- 238000005868 electrolysis reaction Methods 0.000 description 2
- 229910052741 iridium Inorganic materials 0.000 description 2
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 238000004832 voltammetry Methods 0.000 description 2
- 230000004913 activation Effects 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical class Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 238000009713 electroplating Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 238000005272 metallurgy Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000002161 passivation Methods 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
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- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/02—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition
- C23C18/12—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material
- C23C18/1204—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material inorganic material, e.g. non-oxide and non-metallic such as sulfides, nitrides based compounds
- C23C18/1208—Oxides, e.g. ceramics
- C23C18/1216—Metal oxides
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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
- C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
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- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/02—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition
- C23C18/12—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material
- C23C18/125—Process of deposition of the inorganic material
- C23C18/1254—Sol or sol-gel processing
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- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/02—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition
- C23C18/12—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material
- C23C18/125—Process of deposition of the inorganic material
- C23C18/1262—Process of deposition of the inorganic material involving particles, e.g. carbon nanotubes [CNT], flakes
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- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/02—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition
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- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
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- C25B11/055—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the substrate or carrier material
- C25B11/057—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the substrate or carrier material consisting of a single element or compound
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- C25B11/093—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of at least one catalytic element and at least one catalytic compound; consisting of two or more catalytic elements or catalytic compounds at least one noble metal or noble metal oxide and at least one non-noble metal oxide
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Abstract
The invention provides a multi-component oxide coating titanium anode plate and a preparation method thereof, wherein the multi-component oxide coating titanium anode plate takes a pure titanium plate as a substrate, a surface active layer is a multi-component oxide of iridium tantalum molybdenum samarium mixed oxide, and a sol-gel method is taken as a preparation process, rare earth element samarium is introduced on the basis of the iridium tantalum coating, so that the anode oxide can be effectively reducedThe interface resistance between the coating and the electrolytic solution improves the conductivity, thereby improving the electrocatalytic performance of the electrode. The transition metal molybdenum is introduced, so that the density of the surface coating can be increased, the penetration of external active oxygen and electrolyte into the titanium base is avoided or slowed down, and the service life of the electrode is prolonged. Meanwhile, the sol-gel method preparation process is improved, a surfactant is added into a solvent to increase the dispersion effect of metal ions, and nano IrO is used2The powder replaces partial precursor chloroiridic acid to be directly melted in the colloidal solution, so that the coating structure can be improved, and the coating has more excellent electrocatalytic activity and stability.
Description
Technical Field
The invention belongs to the technical field of electrochemistry, and particularly relates to a titanium-based coating titanium anode plate and a preparation method thereof.
Background
The metal oxide coating anode is mainly applied to two industries of electrometallurgy and electrochemistry, and the application fields relate to the aspects of sewage and wastewater treatment, chemical engineering, metallurgy, electroplating, organic synthesis and the like, wherein noble metal iridium has high electrochemical activity and corrosion resistance, is generally regarded as an electrode material, and has great success in a plurality of electrochemical industries, and the iridium tantalum coating titanium anode is known as an ideal anode material in an acid oxygen evolution environment. However, the electrochemical performance and stability of a single iridium tantalum titanium anode cannot meet the application requirements of the current electrode, and other elements are usually added to form a titanium anode with a multi-element oxide active coating.
In the existing preparation method of the titanium anode plate, the thermal oxidation decomposition process is the most common preparation method of the existing noble metal active coating titanium anode due to simple manufacturing flow and low equipment cost, but the required sintering temperature is high, the prepared electrode surface is not uniform enough, the compactness is poor, the electrode is easy to fall off, and the service life and the activation performance are not ideal enough.
Disclosure of Invention
In order to solve the problems, the invention introduces rare earth elements and transition metal elements into an active layer on the basis of an iridium tantalum coating titanium anode, adopts a sol-gel method to prepare the active coating titanium anode, improves the preparation process of the sol-gel method, and discloses a multi-element oxide coating titanium anode plate (Ti-IrO)2+Ta2O5+MoO3+Sm2O3) The method comprises the following steps of taking a titanium plate as a substrate, covering a surface active layer of iridium tantalum molybdenum samarium mixed oxide on the surface of the substrate, wherein the surface active layer is the iridium tantalum molybdenum samarium mixed oxide and comprises the following components in percentage by mass (30.7-32.1): (12.6-13.4): (18.5-19.7): (1.6-2.2) iridium dioxide, tantalum pentoxide, molybdenum trioxide and samarium trioxide.
The preparation method of the titanium anode plate with the multi-component oxide coating comprises the following steps:
s1, pretreatment of the titanium substrate: firstly, sand blasting is carried out to roughen the surface, the primary color of the metal is exposed, then the metal is put into a slightly boiling sodium carbonate solution to remove oil, after the metal is completely washed by clear water, the metal is put into a slightly boiling oxalic acid solution to be etched, and after the etching is finished, the metal is completely washed by the clear water and then put into ethanol for standby application;
s2, preparation of a sol-gel solvent: adding citric acid and a surfactant into a glycol solution, and carrying out ultrasonic treatment to uniformly mix;
s3, preparing the sol-gel coating solution: adding chloroiridic acid, tantalum pentachloride and phosphomolybdic acid into the solvent of S2, heating and stirring to obtain a viscous colloidal solution, adding samarium oxide and nano iridium oxide, and uniformly mixing;
s4, uniformly coating the sol coating solution S3 on the titanium substrate pretreated by S1, drying, putting the titanium substrate into a heat treatment furnace for high-temperature sintering, taking the titanium substrate out after sintering, air-cooling to room temperature, repeating the step S2, coating, drying and sintering for a plurality of times, and annealing at the same temperature to obtain the multi-element oxide coating titanium anode plate (Ti-IrO)2+Ta2O5+MoO3+Sm2O3)。
Preferably, in step S1: the content of sodium carbonate in the sodium carbonate solution is 5% -10%, the oil removing time is 1-2h, the content of oxalic acid in the oxalic acid solution is 10-15%, and the etching time is 2-3 h.
Preferably, in step S2: the addition amount of the citric acid is 19-24% of the total mass of the glycol, and the surfactant is one or more of sulfonate anionic surfactants, mainly comprising sodium alkyl benzene sulfonate, alkyl sulfonate and alpha-sulfo monocarboxylic ester. The addition amount of the surfactant is 7-15% of the total mass of the ethylene glycol, and the ultrasonic treatment time is 10-15 min.
Preferably, in step S3: the stirring heating temperature is 70-80 ℃, the stirring time is 20-40min, and the chloroiridic acid (H)4Cl6IrO), tantalum pentachloride (TaCl)5) Phosphomolybdic acid (H)3PO4·12MoO3) Samarium oxide (Sm)2O3) And nano iridium oxide (IrO)2) The total mass of the catalyst is 21 to 29 percent of ethylene glycol, chloroiridic acid, nano iridium oxide and tantalum pentachlorideThe mass ratio of phosphomolybdic acid to samarium oxide is (21.1-21.5): (4.2-4.7): (10.2-10.9): (9.8-10.4): (0.8-1.1).
Preferably, in step S4: the drying temperature is 100-130 ℃, the drying time is 5-10min, the sintering temperature is 400-450 ℃, the sintering time is 10-15min, the repetition times are 6-10, and the annealing time is 40-80 min.
The invention has the beneficial effects that:
1. compared with the traditional thermal decomposition method, the sol-gel method can uniformly disperse various metal ions in the sol, and the surfactant is added, so that the effect can be improved, when the titanium anode oxide coating is prepared, the required sintering temperature is low, the colloid is uniformly dispersed, the particles on the surface of a finished product are uniform, the number of active points on the surface is increased, and the electrocatalytic activity of the titanium anode is improved to a certain extent.
2. With nano IrO2The powder replaces partial precursor chloroiridic acid to be directly melted in the colloidal solution, and iridium element is introduced into the coating, so that the coating structure can be improved, and the coating has more excellent electrocatalytic activity and stability.
3. After the rare earth element samarium is introduced, the interface resistance between the anode oxide coating and the electrolytic solution can be effectively reduced, and the conductivity is improved, so that the electrocatalytic performance of the electrode is improved, the cracking of the coating can be reduced, and the binding force between the coating and the substrate is increased.
4. After the transition metal molybdenum is introduced, the density of the surface coating can be increased, so that the penetration of external active oxygen and electrolyte into the titanium matrix is avoided or slowed, the passivation of the titanium matrix is avoided or slowed, and the service life of the electrode is prolonged.
Drawings
The invention will now be described, by way of example, with reference to the accompanying drawings, in which:
FIG. 1 is a polarization curve of a titanium anode plate obtained in each example and comparative example;
fig. 2 is a cyclic voltammogram of the titanium anode plate obtained in each example and comparative example.
Detailed Description
The following comparative examples 1 to 5 and examples are now usedExamples 1-3 further illustrate the invention. Comparative example 1 is a single iridium tantalum titanium anode prepared by a general sol-gel method under the condition parameters and the component formula ratio provided by the invention; comparative examples 2-5 based on the components of comparative example 1, comparative example 2 was prepared by adding a surfactant, and comparative example 3 was prepared by nano IrO2Replacing part of chloroiridic acid, doping samarium serving as a rare earth element in a comparative example 4, and doping molybdenum serving as a transition metal element in a comparative example 5; examples 1-3 are the preparation provided by the present invention. The formulation of each component is shown in table 1.
Table 1:
comparative example 1:
the preparation method of the iridium-tantalum coating titanium anode plate A comprises the following steps:
s1, pretreatment of the titanium substrate: firstly, sand blasting is carried out to roughen the surface, the primary color of the metal is exposed, then the metal is put into a slightly boiling 7% sodium carbonate solution to remove oil for 1.5h, after the metal is completely washed by clean water, the metal is put into a slightly boiling 12% oxalic acid solution to be etched for 2.5h, and after the etching is completely washed by clean water, the metal is put into ethanol for standby application.
S2, preparation of sol-gel solvent: 44 parts of citric acid is added to 200 parts of ethylene glycol solution, and ultrasonic treatment is carried out for 12min, so that the mixture is uniformly mixed.
S3, preparation of sol-gel coating liquid: adding 31.7 parts of chloroiridic acid and 13 parts of tantalum pentachloride into the solvent in S2, and heating and stirring at 75 ℃ for 30min to obtain a viscous colloid solution.
S4, uniformly coating the sol coating liquid S3 on the titanium substrate pretreated by S1, drying at 120 ℃ for 7min, putting the titanium substrate into a heat treatment furnace for high-temperature sintering, sintering at 420 ℃ for 12min, taking the titanium substrate out, air-cooling to room temperature, repeating the step S2, coating, drying and sintering for 8 times, and annealing at 420 ℃ for 60min to obtain the iridium tantalum coating titaniumAnode plate (Ti-IrO)2+Ta2O5)。
Comparative example 2:
the titanium anode plate B with the iridium-tantalum coating prepared by adding the surfactant is prepared according to the following steps:
s1, pretreatment of the titanium substrate: firstly, sand blasting is carried out to roughen the surface, the primary color of the metal is exposed, then the metal is put into a slightly boiling 7% sodium carbonate solution to remove oil for 1.5h, after the metal is completely washed by clean water, the metal is put into a slightly boiling 12% oxalic acid solution to be etched for 2.5h, and after the etching is completely washed by clean water, the metal is put into ethanol for standby application.
S2, preparation of sol-gel solvent: 44 parts of citric acid and 20 parts of alkyl sulfonate were added to 200 parts of ethylene glycol solution, and subjected to ultrasonic treatment for 12min to be uniformly mixed.
S3, preparation of sol-gel coating liquid: adding 31.7 parts of chloroiridic acid and 13 parts of tantalum pentachloride into the solvent in S2, and heating and stirring at 75 ℃ for 30min to obtain a viscous colloid solution.
S4, uniformly coating the sol coating liquid S3 on a titanium substrate pretreated by S1, drying at 120 ℃ for 7min, placing the titanium substrate into a heat treatment furnace for high-temperature sintering, sintering at 420 ℃ for 12min, taking out the titanium substrate, air-cooling to room temperature, repeating the step S2, coating, drying and sintering for 8 times, and annealing at 420 ℃ for 60min to obtain an iridium tantalum coating titanium anode plate (Ti-IrO) prepared by adding a surfactant2+Ta2O5)。
Comparative example 3:
this comparative example prepares nano-IrO according to the following procedure2Replacing part of iridium-tantalum coating titanium anode plate C prepared from chloroiridic acid:
s1, pretreatment of the titanium substrate: firstly, sand blasting is carried out to roughen the surface, the primary color of the metal is exposed, then the metal is put into a slightly boiling 7% sodium carbonate solution to remove oil for 1.5h, after the metal is completely washed by clean water, the metal is put into a slightly boiling 12% oxalic acid solution to be etched for 2.5h, and after the etching is completely washed by clean water, the metal is put into ethanol for standby application.
S2, preparation of sol-gel solvent: 44 parts of citric acid is added to 200 parts of ethylene glycol solution, and ultrasonic treatment is carried out for 12min, so that the mixture is uniformly mixed.
S3, preparation of sol-gel coating liquid: adding 26.9 parts of chloroiridic acid and 13 parts of tantalum pentachloride into the solvent described in S2, heating and stirring at 75 ℃ for 30min to obtain a viscous colloidal solution, adding 4.8 parts of nano iridium oxide, and uniformly mixing.
S4, uniformly coating the sol coating solution S3 on a titanium substrate pretreated by S1, drying at 120 ℃ for 7min, placing the titanium substrate into a heat treatment furnace for high-temperature sintering, sintering at 420 ℃ for 12min, taking out the titanium substrate, air-cooling to room temperature, repeating the step S2, coating, drying and sintering for 8 times, and annealing at 420 ℃ for 60min to obtain the nano IrO2Titanium anode plate (Ti-IrO) with iridium tantalum coating prepared by replacing part of chloroiridic acid2+Ta2O5)。
Comparative example 4:
the titanium anode plate D with the iridium tantalum coating prepared by doping the rare earth element samarium is prepared according to the following steps:
s1, pretreatment of the titanium substrate: firstly, sand blasting is carried out to roughen the surface, the primary color of the metal is exposed, then the metal is put into a slightly boiling 7% sodium carbonate solution to remove oil for 1.5h, after the metal is completely washed by clean water, the metal is put into a slightly boiling 12% oxalic acid solution to be etched for 2.5h, and after the etching is completely washed by clean water, the metal is put into ethanol for standby application.
S2, preparation of sol-gel solvent: 44 parts of citric acid is added to 200 parts of ethylene glycol solution, and ultrasonic treatment is carried out for 12min, so that the mixture is uniformly mixed.
S3, preparation of sol-gel coating liquid: adding 31.7 parts of chloroiridic acid and 13 parts of tantalum pentachloride into the solvent described in S2, heating and stirring at 75 ℃ for 30min to obtain a viscous colloidal solution, adding 1 part of samarium oxide, and uniformly mixing.
S4, uniformly coating the sol coating liquid S3 on a titanium substrate pretreated by S1, drying at 120 ℃ for 7min, placing the titanium substrate into a heat treatment furnace for high-temperature sintering, sintering at 420 ℃ for 12min, taking out the titanium substrate, air-cooling to room temperature, repeating the step S2, coating, drying and sintering for 8 times, and annealing at 420 ℃ for 60min to obtain an iridium tantalum coating titanium anode plate (Ti-IrO) doped with rare earth element samarium2+Ta2O5+Sm2O3)。
Comparative example 5:
the titanium anode plate E with the iridium tantalum coating prepared by doping molybdenum with the transition metal element is prepared according to the following steps:
s1, pretreatment of the titanium substrate: firstly, sand blasting is carried out to roughen the surface, the primary color of the metal is exposed, then the metal is put into a slightly boiling 7% sodium carbonate solution to remove oil for 1.5h, after the metal is completely washed by clean water, the metal is put into a slightly boiling 12% oxalic acid solution to be etched for 2.5h, and after the etching is completely washed by clean water, the metal is put into ethanol for standby application.
S2, preparation of sol-gel solvent: 44 parts of citric acid is added to 200 parts of ethylene glycol solution, and ultrasonic treatment is carried out for 12min, so that the mixture is uniformly mixed.
S3, preparation of sol-gel coating liquid: 27.6 parts of chloroiridic acid, 11.2 parts of tantalum pentachloride and 10.7 parts of phosphomolybdic acid are added into the solvent in S2, and the mixture is heated and stirred at 75 ℃ for 30min to obtain a viscous colloidal solution.
S4, uniformly coating the sol coating solution S3 on a titanium substrate pretreated by S1, drying at 120 ℃ for 7min, placing the titanium substrate into a heat treatment furnace for high-temperature sintering, sintering at 420 ℃ for 12min, taking out the titanium substrate, air-cooling to room temperature, repeating the step S2, coating, drying and sintering for 8 times, and annealing at 420 ℃ for 60min to obtain an iridium tantalum coating titanium anode plate (Ti-IrO) doped with transition metal molybdenum2+Ta2O5+MoO3)。
Example 1:
the first group of multi-component oxide coating titanium anode plate F is prepared by the following steps:
s1, pretreatment of the titanium substrate: firstly, sand blasting is carried out to roughen the surface, the primary color of the metal is exposed, then the metal is put into a slightly boiling 7% sodium carbonate solution to remove oil for 1.5h, after the metal is completely washed by clean water, the metal is put into a slightly boiling 12% oxalic acid solution to be etched for 2.5h, and after the etching is completely washed by clean water, the metal is put into ethanol for standby application.
S2, preparation of sol-gel solvent: 44 parts of citric acid and 20 parts of alkyl sulfonate were added to 200 parts of ethylene glycol solution, and subjected to ultrasonic treatment for 12min to be uniformly mixed.
S3, preparation of sol-gel coating liquid: adding 22.8 parts of chloroiridic acid, 11.2 parts of tantalum pentachloride and 10.7 parts of phosphomolybdic acid into the solvent described in S2, heating and stirring at 75 ℃ for 30min to obtain a viscous colloidal solution, adding 1 part of samarium oxide and 4.8 parts of nano iridium oxide, and uniformly mixing.
S4, uniformly coating the sol coating solution S3 on a titanium substrate pretreated by S1, drying for 7min at 120 ℃, putting the titanium substrate into a heat treatment furnace for high-temperature sintering, sintering for 12min at 420 ℃, taking the titanium substrate out, air-cooling to room temperature, repeating the step S2, coating, drying and sintering for 8 times, and annealing for 60min at 420 ℃ to obtain the first group of multi-element oxide coating titanium anode plate (Ti-IrO) of the invention2+Ta2O5+MoO3+Sm2O3)。
Example 2:
the second group of multi-component oxide coating titanium anode plate G is prepared by the following steps:
s1, pretreatment of the titanium substrate: firstly, sand blasting is carried out to roughen the surface, the primary color of the metal is exposed, then the metal is put into a slightly boiling 5% sodium carbonate solution to remove oil for 2 hours, after the metal is completely washed by clean water, the metal is put into a slightly boiling 10% oxalic acid solution to be etched for 3 hours, and after the etching is finished, the metal is completely washed by clean water and then put into ethanol for standby application.
S2, preparation of sol-gel solvent: adding 39 parts of citric acid and 16 parts of sodium alkyl benzene sulfonate into 200 parts of glycol solution, and carrying out ultrasonic treatment for 10min to uniformly mix.
S3, preparation of sol-gel coating liquid: adding 20.1 parts of chloroiridic acid, 9.7 parts of tantalum pentachloride and 9.3 parts of phosphomolybdic acid into the solvent described in S2, heating and stirring at 70 ℃ for 40min to obtain a viscous colloidal solution, adding 0.8 part of samarium oxide and 4.1 parts of nano iridium oxide, and uniformly mixing.
S4, uniformly coating the sol coating solution S3 on a titanium substrate pretreated by S1, drying the titanium substrate for 10min at 100 ℃, putting the titanium substrate into a heat treatment furnace for high-temperature sintering, sintering the titanium substrate for 15min at 400 ℃, taking the titanium substrate out, air-cooling the titanium substrate to room temperature, repeating the step S2, coating, drying and sintering the titanium substrate for 10 times, and annealing the titanium substrate for 40min at 400 ℃ to obtain a second group of multi-component oxide coating titanium anode plate (Ti-IrO)2+Ta2O5+MoO3+Sm2O3)。
Example 3:
the third group of multi-component oxide coating titanium anode plate H is prepared by the following steps:
s1, pretreatment of the titanium substrate: firstly, sand blasting is carried out to roughen the surface, the primary color of the metal is exposed, then the metal is put into a slightly boiling 10% sodium carbonate solution to remove oil for 1 hour, after the metal is completely washed by clear water, the metal is put into a slightly boiling 15% oxalic acid solution to be etched for 2 hours, and after the etching is finished, the metal is completely washed by the clear water and then put into ethanol for standby application.
S2, preparation of sol-gel solvent: adding 48 parts of citric acid and 28 parts of alpha-sulfomonocarboxylic acid ester into 200 parts of ethylene glycol solution, and carrying out ultrasonic treatment for 15min to uniformly mix.
S3, preparation of sol-gel coating liquid: adding 24.8 parts of chloroiridic acid, 12.5 parts of tantalum pentachloride and 12.1 parts of phosphomolybdic acid into the solvent described in S2, heating and stirring at 80 ℃ for 20min to obtain a viscous colloidal solution, adding 1.3 parts of samarium oxide and 5.5 parts of nano iridium oxide, and uniformly mixing.
S4, uniformly coating the sol coating solution S3 on a titanium substrate pretreated by S1, drying for 5min at 130 ℃, putting the titanium substrate into a heat treatment furnace for high-temperature sintering, taking the titanium substrate out after sintering for 10min at 450 ℃, air-cooling to room temperature, repeating the step S2, coating, drying and sintering for 6 times, and annealing at 450 ℃ for 80min to obtain a third group of multi-component oxide coating titanium anode plate (Ti-IrO)2+Ta2O5+MoO3+Sm2O3)。
The following tests were performed on the A, B, C, D, E, F, G, H described above.
And (3) electrochemical performance testing: on the electrochemical workstation, a platinum sheet is used as an auxiliary electrode, a saturated calomel electrode is used as a reference electrode, and the working electrode is the product in the embodiment. Controlling the temperature at 25 ℃ at 0.5mol/L of H2SO4And (3) measuring an anodic polarization curve and a cyclic voltammetry curve of the electrode by adopting a linear scanning technology in the electrolytic solution. The anodic polarization curve is shown in FIG. 1, and the cyclic voltammogram is shown in FIG. 2.
Determination of the enhanced electrolytic life: the product of the embodiment was processed to have an electrode area of 1cm2The sample (2) was a pure titanium sheet as the cathode,the distance between poles is 2cm, and the current density is 20mA/cm2The temperature is controlled at 40 ℃ and is 0.5mol/H2SO4The time for the electrolytic voltage to rise by 10V relative to the initial value of electrolysis in the electrolytic solution is the strengthening life of the electrode. The resulting enhanced electrolytic life is shown in Table 2.
Table 2:
| product(s) | A | B | C | D | E | F | G | H |
| Enhanced electrolytic life/h | 320 | 304 | 422 | 402 | 619 | 627 | 624 | 629 |
From the above table 2, it can be seen that the addition of the surfactant to the solvent of the precursor can slightly reduce the service life of the titanium anode, and the introduction of the transition metal element molybdenum can significantly improve the service life of the titanium anode, and the product F, G, H obtained by the preparation method provided by the present invention has an excellent service life, and the enhanced electrolysis life of the product F is improved by 95.9% compared with that of the product a.
The main information reflected by the polarization curve is the electrocatalytic activity of the electrode, and the smaller the corresponding potential of the polarization curve at the same current density represents the higher electrocatalytic activity, namely the higher oxygen evolution current density is achieved under the same oxygen evolution potential, which indicates that the prepared oxide coating titanium anode has higher oxygen evolution electrocatalytic activity. As can be seen from FIG. 1, the product F, G, H prepared by the preparation method provided by the invention has higher oxygen evolution electrocatalytic activity than the product A, B, C, D, E, and the product D has higher oxygen evolution electrocatalytic activity than the product A, and the introduction of the rare earth element samarium can effectively improve the electrocatalytic activity of the titanium anode.
The voltammetry area surrounded by the cyclic voltammetry curve is in direct proportion to the surface charge capacity of the titanium anode coating, and the larger the area surrounded by the cyclic voltammetry curve is, the larger the voltammetry electric quantity of the oxide anode surface is, the larger the number of active points on the surface is, the larger the electrochemical effective surface area is, and the more stable the electrocatalytic activity of the electrode is. As can be seen from FIG. 2, the effect of the surfactant in the solvent is nanometer IrO2The introduction of rare earth element samarium can improve the electrocatalytic stability of the titanium anode, and under the combined action of the rare earth element samarium and the titanium anode, the product F, G, H prepared by the preparation method provided by the invention has more stable electrocatalytic activity than the product A, B, C, D, E.
Claims (6)
1. A multi-component oxide coating titanium anode plate is characterized in that a titanium plate is used as a substrate, a surface active layer of iridium tantalum molybdenum samarium mixed oxide is coated on the surface of the substrate, and the surface active layer comprises the following components in percentage by mass (30.7-32.1): (12.6-13.4): (18.5-19.7): (1.6-2.2) iridium dioxide, tantalum pentoxide, molybdenum trioxide and samarium trioxide.
2. The method for preparing the titanium anode plate with the multi-oxide coating according to claim 1, which is characterized by comprising the following steps:
s1, pretreatment of the titanium substrate: firstly, sand blasting is carried out to roughen the surface, the primary color of the metal is exposed, then the metal is put into a slightly boiling sodium carbonate solution to remove oil, after the metal is completely washed by clear water, the metal is put into a slightly boiling oxalic acid solution to be etched, and after the etching is finished, the metal is completely washed by the clear water and then put into ethanol for standby application;
s2, preparation of a sol-gel solvent: adding citric acid and a surfactant into a glycol solution, and carrying out ultrasonic treatment to uniformly mix;
s3, preparing the sol-gel coating solution: adding chloroiridic acid, tantalum pentachloride and phosphomolybdic acid into the solvent of S2, heating and stirring to obtain a viscous colloidal solution, adding samarium oxide and nano iridium oxide, and uniformly mixing;
s4, uniformly coating the sol coating liquid S3 on the titanium substrate pretreated by S1, drying, placing the titanium substrate into a heat treatment furnace for high-temperature sintering, taking the titanium substrate out after sintering, air-cooling to room temperature, repeating the step S2, coating, drying, sintering for a plurality of times, and annealing at the same temperature to obtain the multi-element oxide coating titanium anode plate.
3. The method for preparing the titanium anode plate with the multi-oxide coating according to claim 2, wherein in the step S1: the content of sodium carbonate in the sodium carbonate solution is 5% -10%, the oil removing time is 1-2h, the content of oxalic acid in the oxalic acid solution is 10-15%, and the etching time is 2-3 h.
4. The method for preparing the titanium anode plate with the multi-oxide coating according to claim 2, wherein in the step S2: the addition amount of the citric acid is 19-24% of the total mass of the glycol, and the surfactant is one or more of sulfonate anionic surfactants, mainly comprising sodium alkyl benzene sulfonate, alkyl sulfonate and alpha-sulfo monocarboxylic ester. The addition amount of the surfactant is 7-15% of the total mass of the ethylene glycol, and the ultrasonic treatment time is 10-15 min.
5. The method for preparing the titanium anode plate with the multi-oxide coating according to claim 2, wherein in the step S3: the stirring heating temperature is 70-80 ℃, the stirring time is 20-40min, the total mass of the chloroiridic acid, the tantalum pentachloride, the phosphomolybdic acid, the samarium oxide and the nano iridium oxide is 21-29% of that of the ethylene glycol, and the mass ratio of the chloroiridic acid, the nano iridium oxide, the tantalum pentachloride, the phosphomolybdic acid and the samarium oxide is (21.1-21.5): (4.2-4.7): (10.2-10.9): (9.8-10.4): (0.8-1.1).
6. The titanium anode plate with a multi-component oxide coating and the preparation method thereof according to claim 2, wherein in the step of S4: the drying temperature is 100-130 ℃, the drying time is 5-10min, the sintering temperature is 400-450 ℃, the sintering time is 10-15min, the repetition times are 6-10, and the annealing time is 40-80 min.
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| KR20030080536A (en) * | 2002-04-09 | 2003-10-17 | 한국수질개발 주식회사 | Electrode and its manufacturing method using rare earth element |
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| CN109763149A (en) * | 2019-03-12 | 2019-05-17 | 江阴安诺电极有限公司 | Iridium tantalum coated anode plate |
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| KR20030080536A (en) * | 2002-04-09 | 2003-10-17 | 한국수질개발 주식회사 | Electrode and its manufacturing method using rare earth element |
| CN1995464A (en) * | 2006-11-28 | 2007-07-11 | 北京科技大学 | Nanocrystalline iridium series oxide coating electrode preparation method |
| CN106367777A (en) * | 2016-12-14 | 2017-02-01 | 青岛双瑞海洋环境工程股份有限公司 | Oxide anode material suitable for low salinity seawater environment and preparation process thereof |
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