CN110655150B - Titanium-based tin oxide anode electrode and preparation method thereof - Google Patents
Titanium-based tin oxide anode electrode and preparation method thereof Download PDFInfo
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- CN110655150B CN110655150B CN201810691711.6A CN201810691711A CN110655150B CN 110655150 B CN110655150 B CN 110655150B CN 201810691711 A CN201810691711 A CN 201810691711A CN 110655150 B CN110655150 B CN 110655150B
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- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 title claims abstract description 98
- 239000010936 titanium Substances 0.000 title claims abstract description 97
- 229910052719 titanium Inorganic materials 0.000 title claims abstract description 97
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 title claims abstract description 90
- 229910001887 tin oxide Inorganic materials 0.000 title claims abstract description 90
- 238000002360 preparation method Methods 0.000 title abstract description 9
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 68
- 238000000576 coating method Methods 0.000 claims abstract description 64
- 239000011248 coating agent Substances 0.000 claims abstract description 60
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 34
- 239000010949 copper Substances 0.000 claims abstract description 33
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 32
- 229910052802 copper Inorganic materials 0.000 claims abstract description 32
- 229910052787 antimony Inorganic materials 0.000 claims abstract description 24
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 claims abstract description 24
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000001301 oxygen Substances 0.000 claims abstract description 7
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 7
- 239000002243 precursor Substances 0.000 claims description 23
- 238000001035 drying Methods 0.000 claims description 22
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 16
- 239000000758 substrate Substances 0.000 claims description 15
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 14
- 239000011135 tin Substances 0.000 claims description 12
- 229910052718 tin Inorganic materials 0.000 claims description 12
- 238000001354 calcination Methods 0.000 claims description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 10
- 239000011159 matrix material Substances 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 6
- 230000003197 catalytic effect Effects 0.000 claims description 5
- YOCUPQPZWBBYIX-UHFFFAOYSA-N copper nickel Chemical compound [Ni].[Cu] YOCUPQPZWBBYIX-UHFFFAOYSA-N 0.000 claims description 5
- 239000008367 deionised water Substances 0.000 claims description 5
- 229910021641 deionized water Inorganic materials 0.000 claims description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
- 230000003647 oxidation Effects 0.000 claims description 5
- 238000007254 oxidation reaction Methods 0.000 claims description 5
- 239000004408 titanium dioxide Substances 0.000 claims description 3
- 238000004140 cleaning Methods 0.000 claims description 2
- 239000000463 material Substances 0.000 claims description 2
- 239000002957 persistent organic pollutant Substances 0.000 claims description 2
- 239000010815 organic waste Substances 0.000 claims 1
- 229910021607 Silver chloride Inorganic materials 0.000 abstract description 4
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 abstract description 4
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- 230000002035 prolonged effect Effects 0.000 abstract description 3
- 239000000126 substance Substances 0.000 abstract description 3
- 238000005728 strengthening Methods 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 31
- 238000003756 stirring Methods 0.000 description 15
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 12
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 description 12
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 description 12
- 238000005303 weighing Methods 0.000 description 12
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 10
- 230000001680 brushing effect Effects 0.000 description 8
- 238000007598 dipping method Methods 0.000 description 8
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 7
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 7
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 7
- 238000001816 cooling Methods 0.000 description 6
- 238000005488 sandblasting Methods 0.000 description 6
- 238000005245 sintering Methods 0.000 description 6
- 239000002904 solvent Substances 0.000 description 5
- 239000002351 wastewater Substances 0.000 description 5
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 229910000510 noble metal Inorganic materials 0.000 description 4
- 235000006408 oxalic acid Nutrition 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000011010 flushing procedure Methods 0.000 description 3
- 239000004576 sand Substances 0.000 description 3
- 238000004506 ultrasonic cleaning Methods 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- 229910052741 iridium Inorganic materials 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- 231100000331 toxic Toxicity 0.000 description 2
- 230000002588 toxic effect Effects 0.000 description 2
- 229910001069 Ti alloy Inorganic materials 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 150000001555 benzenes Chemical class 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 230000000711 cancerogenic effect Effects 0.000 description 1
- 231100000315 carcinogenic Toxicity 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 230000000813 microbial effect Effects 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 125000005575 polycyclic aromatic hydrocarbon group Chemical group 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 231100000378 teratogenic Toxicity 0.000 description 1
- 230000003390 teratogenic effect Effects 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- 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
- C02F1/467—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis by electrochemical disinfection; by electrooxydation or by electroreduction
- C02F1/4672—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis by electrochemical disinfection; by electrooxydation or by electroreduction by electrooxydation
-
- C—CHEMISTRY; METALLURGY
- 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
- C02F1/46104—Devices therefor; Their operating or servicing
- C02F1/46109—Electrodes
-
- C—CHEMISTRY; METALLURGY
- 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
- C02F1/46104—Devices therefor; Their operating or servicing
- C02F1/46109—Electrodes
- C02F2001/46133—Electrodes characterised by the material
- C02F2001/46138—Electrodes comprising a substrate and a coating
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Organic Chemistry (AREA)
- Conductive Materials (AREA)
- Chemically Coating (AREA)
Abstract
The invention discloses a novel titanium-based tin oxide anode electrode and a preparation method thereof. The chemical stability of the titanium-based tin oxide positive electrode is improved by utilizing the nickel and copper co-doped tin oxide coating, and the multi-layer nickel and copper co-doped tin oxide coating and the antimony doped tin oxide coating are constructed, so that the high oxygen evolution potential of the tin oxide positive electrode is ensured, the service life of the titanium-based tin oxide positive electrode is greatly prolonged, the oxygen evolution potential of the novel tin oxide positive electrode is more than 2.0V (reference silver chloride reference electrode) and the strengthening service life is more than 20 hours. The electrode has the advantages of simple preparation process, low cost, low equipment requirement, easy control of operation and easy industrialized mass production.
Description
Technical Field
The invention belongs to the field of anode electrodes for treating industrial organic wastewater by electrochemical catalytic oxidation, and relates to a titanium-based tin oxide anode electrode and a preparation method thereof
Background
The pollution problem of industrial organic wastewater is increasingly serious, and especially toxic and harmful organic matters contained in water, such as phenols, benzenes, polycyclic aromatic hydrocarbons and the like, have organic matters with carcinogenic and teratogenic harm and directly threaten the health of people in China. The electrochemical catalytic oxidation treatment of organic wastewater is considered as the most promising industrial organic wastewater treatment process because of the capability of effectively degrading high-concentration and microbial degradation-resistant toxic and harmful organic matters and no secondary pollution. The kind of the anode electrode determines the technology of electrochemical catalytic oxidation treatment of industrial organic wastewater, including degradation efficiency of organic matters, formation of organic matters by-products and the like. The titanium-based tin oxide anode electrode has low price, high COD removal rate and high current efficiency, and is the most potential anode electrode. However, the very short service life limits the commercial development of titanium-based tin oxide anode electrodes. Although the service life of the tin oxide anode electrode can be greatly prolonged by doping noble metal elements such as Ir, ru and the like, the noble metal element doping not only increases the manufacturing cost of the tin oxide anode electrode, but also greatly reduces the electrocatalytic property of the tin oxide anode electrode. All the defects result in that the tin oxide anode electrode doped with noble metal elements such as Ir, ru and the like is not suitable for large-scale application in the sewage treatment industry.
Disclosure of Invention
The invention aims to solve the problem that the service life of the existing titanium-based tin oxide anode electrode is low, and provides a non-noble metal element doping method for prolonging the service life of the titanium-based tin oxide anode electrode. The anode is prepared by depositing a nickel and copper co-doped antimony doped tin oxide coating on a titanium substrate. The tin oxide chemical stability is improved by doping nickel, copper and antimony elements, so that the titanium-based tin oxide positive electrode is obtained, and the titanium-based tin oxide positive electrode has a high oxygen evolution potential of 2.0V (reference silver chloride reference electrode) and also has a long service life.
The titanium-based tin oxide anode electrode is structured in such a way that a first layer is a titanium substrate, a second layer is a nickel and copper co-doped tin oxide coating and a third layer is an antimony doped tin oxide coating.
The titanium matrix is titanium metal with all specifications, such as titanium foil, titanium plate, titanium net, titanium alloy and the like;
the titanium matrix can be of any geometric shape, such as square, cylindrical, porous and the like;
the nickel and copper co-doped tin oxide coating and the antimony doped tin oxide coating are crystalline coatings;
the thickness of the nickel and copper co-doped tin oxide coating is 5-10 mu m;
the thickness of the antimony doped tin oxide coating is more than 20 mu m;
the doping concentration (mol%) of nickel and copper in the nickel and copper co-doped tin oxide coating is 3% -20%.
Another object of the present invention is to provide a method for preparing the above titanium-based tin oxide anode electrode, comprising the steps of:
1) Taking a titanium matrix as a supporting material of a nickel and copper co-doped tin oxide coating and an antimony doped tin oxide coating; removing organic pollutants such as oil stains and the like on the surface of the titanium substrate and a titanium dioxide film, and finally cleaning the titanium substrate with alcohol and deionized water in sequence, and then quickly drying the titanium substrate with nitrogen for later use;
2) Preparing a precursor solution containing tin, nickel and copper and a precursor solution containing tin and antimony;
3) Coating a precursor solution containing tin, nickel and copper on the surface of a titanium substrate, drying and calcining the precursor solution, and repeating the steps for a plurality of times to obtain a titanium-based nickel and copper co-doped tin oxide coating;
4) And (3) coating a precursor solution containing tin and antimony on the titanium-based nickel and copper co-doped tin oxide coating, drying and calcining the coating, and repeating the steps for a plurality of times to finally obtain the long-service-life titanium-based tin oxide anode electrode.
The organic matters on the surface of the titanium matrix are removed by adopting an organic solvent or alkali liquor, such as alcohol, sodium hydroxide and the like;
the titanium dioxide film on the surface of the titanium matrix is removed, and acid is adopted to remove corrosion of the titanium matrix, such as hydrochloric acid, oxalic acid and the like;
the preparation of the precursor solution containing tin and nickel comprises the steps of dissolving tin, nickel chloride and copper nitrate in a solvent, wherein the solvent is absolute alcohol and IPA solvent, and the proportion of IPA is 10-30%;
the preparation of the precursor solution containing tin and antimony is to dissolve the chloride containing tin and antimony in a solvent, wherein the solvent is absolute alcohol;
the precursor solution containing tin, nickel and copper is coated on the surface of the titanium substrate, and the coating process can be any coating process such as dipping coating, brushing coating, spraying coating and the like;
the precursor solution containing tin and antimony is coated on the surface of the titanium-based nickel and copper co-doped tin oxide coating, and can be prepared by all coating processes such as dipping coating, brushing coating, spraying coating and the like;
the drying temperature is 80-100 ℃.
The calcining temperature is 600-700 ℃.
The titanium-based tin oxide anode electrode is used for treating industrial organic wastewater through electrochemical catalytic oxidation.
The beneficial effects of the invention are as follows: the invention provides a titanium-based tin oxide positive electrode and a preparation method thereof, wherein the chemical stability of the titanium-based tin oxide positive electrode is improved by utilizing a nickel and copper co-doped tin oxide coating, a multi-layer nickel and copper co-doped tin oxide coating and an antimony doped tin oxide coating are constructed, the service life of the titanium-based tin oxide positive electrode is greatly prolonged while the high oxygen evolution potential of the tin oxide positive electrode is ensured, and the oxygen evolution potential of the tin oxide positive electrode is more than 2.0V (reference silver chloride reference electrode) and the strengthening service life is more than 20 hours. The electrode has the advantages of simple preparation process, low cost, low equipment requirement, easy control of operation and easy industrialized mass production.
Drawings
FIG. 1 is a schematic structural diagram of a titanium-based tin oxide anode electrode with long service life, wherein 1 is a titanium substrate, 2 is a nickel-copper co-doped tin oxide coating, and 3 is an antimony-doped tin oxide coating;
FIG. 2 is a scanning electron microscope image of a long life titanium-based tin oxide anode electrode of the present invention;
FIG. 3 is a graph showing the test of oxygen evolution potential of a long life titanium-based tin oxide anode electrode of the present invention in 0.5M sulfuric acid aqueous solution;
FIG. 4 is a graph of accelerated life test of a long life titanium-based tin oxide anode electrode of the present invention under the following conditions: the current density of the anode electrode is 500mA/cm 2 The electrolyte solution is sulfuric acid with the concentration of 0.5M, and the area of the titanium-based tin oxide anode electrode is 1cm 2 Area of 1cm 2 The Pt electrode of (c) was a counter electrode, a reference silver chloride reference electrode. (1) The titanium-based tin oxide anode electrode is obtained by directly coating an antimony doped tin oxide electrode on a titanium plate, and (2) coating a nickel and copper co-doped tin oxide coating and then coating the antimony doped tin oxide. Fig. 4 shows that the tin oxide anode of the present invention has a longer service life.
Detailed Description
The following describes in detail the embodiments of the present invention, which are implemented on the premise of the technical solution of the present invention, and detailed implementation and specific operation procedures are given, but the protection scope of the present invention is not limited to the following embodiments.
The titanium-based tin oxide anode electrode with long service life comprises a titanium substrate, and a nickel-copper co-doped tin oxide coating and an antimony-doped tin oxide coating which are sequentially covered on the surface of the titanium substrate.
Example 1:
the embodiment comprises the following steps:
step (1), as shown in figure 1, the thickness is 1mm, and the area is 9cm 2 The titanium plate is used as a titanium matrix, the surface of the titanium plate is subjected to texturing treatment by a sand blasting process, and the size of sand grains is 300 meshes. Putting the titanium plate subjected to sand blasting into an alcohol solution for ultrasonic cleaning for 10 minutes, then corroding the cleaned titanium plate with 10% oxalic acid for 30 minutes, then flushing the corroded titanium plate with deionized water, and finally drying the titanium plate by utilizing nitrogen.
And (2) weighing 8.0g of stannic chloride, putting the stannic chloride into 20-50mL of alcohol, and fully stirring for 30 minutes by using a magnetic stirrer for later use.
And (3) weighing 0.8g of nickel chloride, putting the nickel chloride into the solution obtained in the step (2), and fully stirring for 30 minutes by using a magnetic stirrer for later use.
And (4) weighing 1.2g of copper nitrate, putting the copper nitrate into the solution obtained in the step 3, and fully stirring the copper nitrate for 30 minutes by using a magnetic stirrer for later use.
And (5) adding 10% of IPA into the solution obtained in the step 4, and fully stirring for 20 minutes by using a magnetic stirrer for later use.
And (6) dipping the precursor solution obtained in the step (5) by using a brush, brushing the precursor solution on the surface of the titanium plate obtained in the step (1) uniformly, and then putting the titanium plate into a drying oven at 100 ℃ for drying for 10 minutes.
And (7) placing the titanium plate obtained in the step 6 into a sintering furnace with the temperature of 650 ℃ for calcination for 10 minutes, and taking out and cooling.
And (8) repeating the step 6 and the step 7 for 5-10 times, so that the thickness of the nickel and copper co-doped tin oxide coating reaches more than 5 microns.
And (9) weighing 6.0g of stannic chloride and 0.6g of antimonic chloride, putting the weighed stannic chloride and antimonic chloride into 40mL of alcohol, and fully stirring for 30 minutes by using a magnetic stirrer for later use.
And (10) dipping the precursor solution obtained in the step (9) by using a brush, uniformly brushing the surface of the titanium-based nickel and copper co-doped tin oxide coating obtained in the step (7), and then putting the surface into a drying oven at 100 ℃ for drying for 10 minutes.
And (11) placing the antimony doped tin oxide coating obtained in the step (10) into a sintering furnace with the temperature of 650 ℃ for calcination for 10 minutes, and then taking out and cooling.
And (12) repeating the steps 10 and 11 for 20-25 times, so that the thickness of the antimony doped tin oxide coating reaches more than 20 microns.
Example 2:
the embodiment comprises the following steps:
step (1), as shown in figure 1, the thickness is 1mm, and the area is 9cm 2 The titanium plate is used as a titanium matrix, the surface of the titanium plate is subjected to texturing treatment by a sand blasting process, and the size of sand grains is 300 meshes. Putting the titanium plate subjected to sand blasting into an alcohol solution for ultrasonic cleaning for 10 minutes, then corroding the cleaned titanium plate with 10% oxalic acid for 30 minutes, then flushing the corroded titanium plate with deionized water, and finally drying the titanium plate by utilizing nitrogen.
And (2) weighing 8.0g of stannic chloride, putting the stannic chloride into 20-50mL of alcohol, and fully stirring for 30 minutes by using a magnetic stirrer for later use.
And (3) weighing 0.8g of nickel chloride, putting the nickel chloride into the solution obtained in the step (2), and fully stirring for 30 minutes by using a magnetic stirrer for later use.
And (4) weighing 1.4g of copper nitrate, putting the copper nitrate into the solution obtained in the step 3, and fully stirring the copper nitrate for 30 minutes by using a magnetic stirrer for later use.
And (5) adding 25% of IPA into the solution obtained in the step 4, and fully stirring for 20 minutes by using a magnetic stirrer for later use.
And (6) dipping the precursor solution obtained in the step (5) by using a brush, brushing the precursor solution on the surface of the titanium plate obtained in the step (1) uniformly, and then putting the titanium plate into a drying oven at 100 ℃ for drying for 10 minutes.
And (7) placing the titanium plate obtained in the step 6 into a sintering furnace with the temperature of 650 ℃ for calcination for 10 minutes, and taking out and cooling.
And (8) repeating the step 6 and the step 7 for 5-10 times, so that the thickness of the nickel and copper co-doped tin oxide coating reaches more than 5 microns.
And (9) weighing 6.0g of stannic chloride and 0.6g of antimonic chloride, putting the weighed stannic chloride and antimonic chloride into 40mL of alcohol, and fully stirring for 30 minutes by using a magnetic stirrer for later use.
And (10) dipping the precursor solution obtained in the step (9) by using a brush, uniformly brushing the surface of the titanium-based nickel and copper co-doped tin oxide coating obtained in the step (7), and then putting the surface into a drying oven at 100 ℃ for drying for 10 minutes.
And (11) placing the antimony doped tin oxide coating obtained in the step 9 into a sintering furnace with the temperature of 650 ℃ for calcination for 10 minutes, and then taking out and cooling.
And (12) repeating the steps 10 and 11 for 20-25 times, so that the thickness of the antimony doped tin oxide coating reaches more than 20 microns.
Example 3:
the embodiment comprises the following steps:
step (1), as shown in figure 1, the thickness is 1mm, and the area is 9cm 2 The titanium plate is used as a titanium matrix, the surface of the titanium plate is subjected to texturing treatment by a sand blasting process, and the size of sand grains is 300 meshes. Putting the titanium plate subjected to sand blasting into an alcohol solution for ultrasonic cleaning for 10 minutes, then corroding the cleaned titanium plate with 10% oxalic acid for 30 minutes, then flushing the corroded titanium plate with deionized water, and finally drying the titanium plate by utilizing nitrogen.
And (2) weighing 8.0g of stannic chloride, putting the stannic chloride into 20-50mL of alcohol, and fully stirring for 30 minutes by using a magnetic stirrer for later use.
And (3) weighing 1.5g of nickel chloride, putting the nickel chloride into the solution obtained in the step (2), and fully stirring for 30 minutes by using a magnetic stirrer for later use.
And (4) weighing 1.4g of copper nitrate, putting the copper nitrate into the solution obtained in the step 3, and fully stirring the copper nitrate for 30 minutes by using a magnetic stirrer for later use.
And (5) adding 25% of IPA into the solution obtained in the step 4, and fully stirring for 20 minutes by using a magnetic stirrer for later use.
And (6) dipping the precursor solution obtained in the step (5) by using a brush, brushing the precursor solution on the surface of the titanium plate obtained in the step (1) uniformly, and then putting the titanium plate into a drying oven at 100 ℃ for drying for 10 minutes.
And (7) placing the titanium plate obtained in the step 6 into a sintering furnace with the temperature of 650 ℃ for calcination for 10 minutes, and taking out and cooling.
And (8) repeating the step 6 and the step 7 for 5-10 times, so that the thickness of the nickel and copper co-doped tin oxide coating reaches more than 5 microns.
And (9) weighing 6.0g of stannic chloride and 0.6g of antimonic chloride, putting the weighed stannic chloride and antimonic chloride into 40mL of alcohol, and fully stirring for 30 minutes by using a magnetic stirrer for later use.
And (10) dipping the precursor solution obtained in the step (9) by using a brush, uniformly brushing the surface of the titanium-based nickel and copper co-doped tin oxide coating obtained in the step (7), and then putting the surface into a drying oven at 100 ℃ for drying for 10 minutes.
And (11) placing the antimony doped tin oxide coating obtained in the step 9 into a sintering furnace with the temperature of 650 ℃ for calcination for 10 minutes, and then taking out and cooling.
And (12) repeating the steps 10 and 11 for 20-25 times, so that the thickness of the antimony doped tin oxide coating reaches more than 20 microns.
What is not described in detail in the present specification belongs to the prior art known to those skilled in the art. The above-described embodiments are not intended to limit the present invention, and any modifications and variations made thereto are within the spirit of the present invention and the scope of the appended claims.
Claims (5)
1. A titanium-based tin oxide anode electrode is characterized in that a nickel-copper co-doped tin oxide coating and an antimony-doped tin oxide coating are sequentially coated on a titanium substrate; the nickel doping concentration mol% in the nickel and copper co-doped tin oxide coating is 15-20%.
2. The method for preparing a titanium-based tin oxide anode electrode according to claim 1, comprising the steps of:
1) Taking a titanium matrix as a supporting material of a nickel and copper co-doped tin oxide coating and an antimony doped tin oxide coating; removing oil stain organic pollutants and a titanium dioxide film on the surface of a titanium substrate, and finally cleaning the titanium substrate with alcohol and deionized water in sequence, and then quickly drying the titanium substrate with nitrogen for later use;
2) Preparing a precursor solution containing tin, nickel and copper and a precursor solution containing tin and antimony;
3) Coating a precursor solution containing tin, nickel and copper on the surface of a titanium substrate, drying and calcining the precursor solution, and repeating the steps for a plurality of times to obtain a titanium-based nickel and copper co-doped tin oxide coating;
4) And (3) coating a precursor solution containing tin and antimony on the surface of the titanium-based nickel and copper doped tin oxide coating, drying and calcining the titanium-based nickel and copper doped tin oxide coating for multiple times, and finally obtaining the titanium-based tin oxide anode electrode with high oxygen evolution potential and long service life.
3. A titanium-based tin oxide anode as claimed in claim 1, wherein the nickel-copper co-doped tin oxide coating is an intermediate layer of the anode.
4. A titanium-based tin oxide anode according to claim 1, wherein the Cu doping concentration in the nickel-copper co-doped tin oxide coating is 18-20 mol%.
5. Use of a titanium-based tin oxide anode according to claim 1 for electrochemical catalytic oxidation treatment of industrial organic waste water.
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