CN114988529B - Preparation method of DSA electrode coated with titanium oxide coating on surface - Google Patents
Preparation method of DSA electrode coated with titanium oxide coating on surface Download PDFInfo
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- CN114988529B CN114988529B CN202210650689.7A CN202210650689A CN114988529B CN 114988529 B CN114988529 B CN 114988529B CN 202210650689 A CN202210650689 A CN 202210650689A CN 114988529 B CN114988529 B CN 114988529B
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- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title claims abstract description 141
- 239000011248 coating agent Substances 0.000 title claims abstract description 79
- 238000000576 coating method Methods 0.000 title claims abstract description 79
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 title claims abstract description 19
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 238000007745 plasma electrolytic oxidation reaction Methods 0.000 claims abstract description 48
- 239000010936 titanium Substances 0.000 claims abstract description 46
- 239000004408 titanium dioxide Substances 0.000 claims abstract description 42
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 39
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 35
- 238000001354 calcination Methods 0.000 claims abstract description 20
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 20
- 238000000034 method Methods 0.000 claims abstract description 20
- 239000000758 substrate Substances 0.000 claims abstract description 14
- 238000005507 spraying Methods 0.000 claims abstract description 11
- 238000005336 cracking Methods 0.000 claims abstract description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 3
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 3
- 239000003792 electrolyte Substances 0.000 claims description 44
- 239000000843 powder Substances 0.000 claims description 28
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 18
- 239000002270 dispersing agent Substances 0.000 claims description 16
- 238000001035 drying Methods 0.000 claims description 16
- 239000000654 additive Substances 0.000 claims description 14
- 230000000996 additive effect Effects 0.000 claims description 14
- 239000007789 gas Substances 0.000 claims description 13
- 239000000203 mixture Substances 0.000 claims description 13
- 239000004094 surface-active agent Substances 0.000 claims description 13
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 12
- 239000001257 hydrogen Substances 0.000 claims description 12
- 229910052739 hydrogen Inorganic materials 0.000 claims description 12
- 229910052757 nitrogen Inorganic materials 0.000 claims description 12
- 239000012298 atmosphere Substances 0.000 claims description 11
- 238000001816 cooling Methods 0.000 claims description 10
- 238000007254 oxidation reaction Methods 0.000 claims description 10
- 230000009467 reduction Effects 0.000 claims description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 9
- 230000008569 process Effects 0.000 claims description 9
- 238000010438 heat treatment Methods 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 8
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 7
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 6
- 239000000395 magnesium oxide Substances 0.000 claims description 6
- 239000002202 Polyethylene glycol Substances 0.000 claims description 5
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 5
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 claims description 5
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims description 5
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 claims description 5
- 239000011976 maleic acid Substances 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims description 5
- 239000011858 nanopowder Substances 0.000 claims description 5
- 229920001223 polyethylene glycol Polymers 0.000 claims description 5
- 239000010935 stainless steel Substances 0.000 claims description 5
- 229910001220 stainless steel Inorganic materials 0.000 claims description 5
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 claims description 5
- 229920001732 Lignosulfonate Polymers 0.000 claims description 4
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 claims description 4
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 3
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 3
- 239000004327 boric acid Substances 0.000 claims description 3
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 claims description 2
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 2
- RUPBZQFQVRMKDG-UHFFFAOYSA-M Didecyldimethylammonium chloride Chemical compound [Cl-].CCCCCCCCCC[N+](C)(C)CCCCCCCCCC RUPBZQFQVRMKDG-UHFFFAOYSA-M 0.000 claims description 2
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 claims description 2
- 229910019142 PO4 Inorganic materials 0.000 claims description 2
- 229920002873 Polyethylenimine Polymers 0.000 claims description 2
- 235000021355 Stearic acid Nutrition 0.000 claims description 2
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 claims description 2
- -1 alkyl quaternary ammonium salt Chemical class 0.000 claims description 2
- 239000001768 carboxy methyl cellulose Substances 0.000 claims description 2
- 238000004140 cleaning Methods 0.000 claims description 2
- 229960004670 didecyldimethylammonium chloride Drugs 0.000 claims description 2
- 238000003618 dip coating Methods 0.000 claims description 2
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims description 2
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 claims description 2
- 239000002245 particle Substances 0.000 claims description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 2
- 239000010452 phosphate Substances 0.000 claims description 2
- 230000000630 rising effect Effects 0.000 claims description 2
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 claims description 2
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 claims description 2
- 239000008117 stearic acid Substances 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims description 2
- 229960005196 titanium dioxide Drugs 0.000 claims 10
- 239000011247 coating layer Substances 0.000 claims 1
- 239000010410 layer Substances 0.000 abstract description 16
- 230000000694 effects Effects 0.000 abstract description 9
- 230000007797 corrosion Effects 0.000 abstract description 4
- 238000005260 corrosion Methods 0.000 abstract description 4
- 239000011159 matrix material Substances 0.000 abstract description 4
- 239000002957 persistent organic pollutant Substances 0.000 abstract description 4
- 239000002344 surface layer Substances 0.000 abstract description 4
- 230000000593 degrading effect Effects 0.000 abstract description 3
- 230000005518 electrochemistry Effects 0.000 abstract description 2
- 230000004888 barrier function Effects 0.000 abstract 1
- 238000010525 oxidative degradation reaction Methods 0.000 abstract 1
- 239000002351 wastewater Substances 0.000 description 16
- 230000036284 oxygen consumption Effects 0.000 description 15
- 239000000126 substance Substances 0.000 description 15
- 238000006056 electrooxidation reaction Methods 0.000 description 12
- 230000003647 oxidation Effects 0.000 description 6
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 5
- 229910003481 amorphous carbon Inorganic materials 0.000 description 5
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 4
- 229910052938 sodium sulfate Inorganic materials 0.000 description 4
- 235000011152 sodium sulphate Nutrition 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 3
- 230000010718 Oxidation Activity Effects 0.000 description 3
- 239000004115 Sodium Silicate Substances 0.000 description 3
- 229910001069 Ti alloy Inorganic materials 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 239000013527 degreasing agent Substances 0.000 description 3
- 238000005237 degreasing agent Methods 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 238000005868 electrolysis reaction Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 229920000609 methyl cellulose Polymers 0.000 description 3
- 239000001923 methylcellulose Substances 0.000 description 3
- 229910052708 sodium Inorganic materials 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- 239000001488 sodium phosphate Substances 0.000 description 3
- 229910000162 sodium phosphate Inorganic materials 0.000 description 3
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 3
- 229910052911 sodium silicate Inorganic materials 0.000 description 3
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 description 3
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 239000010405 anode material Substances 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 239000002159 nanocrystal Substances 0.000 description 2
- 239000005416 organic matter Substances 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 238000005245 sintering Methods 0.000 description 2
- 229910006404 SnO 2 Inorganic materials 0.000 description 1
- 230000003416 augmentation Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910021538 borax Inorganic materials 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000008199 coating composition Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000007731 hot pressing Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 238000009766 low-temperature sintering Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 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
- 239000010815 organic waste Substances 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- 238000007750 plasma spraying Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- FQENQNTWSFEDLI-UHFFFAOYSA-J sodium diphosphate Chemical compound [Na+].[Na+].[Na+].[Na+].[O-]P([O-])(=O)OP([O-])([O-])=O FQENQNTWSFEDLI-UHFFFAOYSA-J 0.000 description 1
- 229940048086 sodium pyrophosphate Drugs 0.000 description 1
- 235000010339 sodium tetraborate Nutrition 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 235000019818 tetrasodium diphosphate Nutrition 0.000 description 1
- 239000001577 tetrasodium phosphonato phosphate Substances 0.000 description 1
- 238000007751 thermal spraying Methods 0.000 description 1
- 230000036962 time dependent Effects 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 230000001131 transforming effect Effects 0.000 description 1
- BSVBQGMMJUBVOD-UHFFFAOYSA-N trisodium borate Chemical compound [Na+].[Na+].[Na+].[O-]B([O-])[O-] BSVBQGMMJUBVOD-UHFFFAOYSA-N 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
- C02F1/46104—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
- C02F1/467—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
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
-
- 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
- C02F2001/46142—Catalytic 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
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2209/00—Controlling or monitoring parameters in water treatment
- C02F2209/08—Chemical Oxygen Demand [COD]; Biological Oxygen Demand [BOD]
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/02—Specific form of oxidant
- C02F2305/023—Reactive oxygen species, singlet oxygen, OH radical
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W10/00—Technologies for wastewater treatment
- Y02W10/30—Wastewater or sewage treatment systems using renewable energies
- Y02W10/37—Wastewater or sewage treatment systems using renewable energies using solar energy
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (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)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
The invention discloses a preparation method of a DSA electrode with a titanium dioxide coating on the surface, and belongs to the technical field of electrochemistry. The method comprises the following steps: micro-arc oxidation is carried out on the titanium substrate to form a titanium oxide coating; calcining in a muffle furnace to convert amorphous titanium dioxide and anatase titanium dioxide in the coating into rutile titanium dioxide; finally spraying a reducing agent on the surface of the coating, cracking the reducing agent into carbon in a high-temperature environment, and converting rutile titanium dioxide into titanium dioxide to obtain the titanium dioxide DSA electrode. The invention adopts the micro-arc oxidation method to prepare the titanium dioxide coating with porous surface layer and compact structure inside, the porous surface layer structure increases the contact area between the electrode and the organic pollutant, the effect of degrading organic pollutants is improved, and the inner layer compact structure has metallurgical bonding force with a matrix, has good barrier property and avoids corrosion to a substrate. The prepared titanium-based titanium oxide electrode has higher activity of electrochemical oxidative degradation of organic matters.
Description
Technical Field
The invention relates to the technical field of electrochemistry, in particular to a preparation method of a DSA electrode with a titanium dioxide coating on the surface.
Background
At present, the catalytic oxidation performance of the electrocatalytic anode material or the generation of strong oxidative hydroxyl free radicals can oxidize organic wastes in water, so that the decomposition and the removal of organic matters are realized, and the method is a development trend of high-organic matter wastewater treatment. The electrochemical oxidation method has the advantages of easy automation, high equipment integration level and no secondary pollution in the aspect of treating high-organic wastewater, so that the electrochemical oxidation method has incomparable advantages of other oxidation technologies. Electrochemical oxidation requires that the electrode has high chemical inertness, high potential window and other performances, and in recent years, research at home and abroad prepares electrocatalytic anodes with various high potential windows, such as PbO 2 Electrode, sb-SnO 2 Electrodes, BDD electrodes, etc.
Titanium suboxide is a titanium dioxide which realizes oxygen vacancies, i.e. Ti, within the titanium dioxide lattice n O 2n-1 Wherein n is more than or equal to 4 and less than or equal to 10, n is an integer, thereby having conductivity, wherein Ti 4 O 7 The conductivity is optimal. Meanwhile, titanium dioxide has a high oxygen evolution potential, which makes it excellent in electrochemical activity. In addition, the titanium dioxide has high electrochemical stability and high corrosion resistance. Titanium suboxide is therefore a desirable electrochemically oxidizing anode material. The main preparation method of the titanium dioxide electrode mainly comprises three technical schemes: scheme one: mixing titanium dioxide powder, water and organic solvent, press forming, and then in reducing atmosphereReducing and sintering to form electrode; scheme II: firstly preparing titanium dioxide powder, mixing the titanium dioxide powder with an adhesive, and then compacting the mixture to prepare an electrode; scheme III: firstly preparing titanium dioxide powder, and then adopting thermal spraying means such as plasma spraying and the like to spray the titanium dioxide on the surface of the substrate to prepare the electrode. The electrode prepared by the scheme one has more holes, the coating is easy to be eroded and destroyed by gas, and the service life is shorter; the electrode prepared in the second scheme has poor conductivity due to the influence of the adhesive; the electrode prepared in the third scheme has more holes on the surface, the substrate is easy to corrode in the electrolysis process, and the binding force of the coating is poor. In general, the existing coating scheme has the defects of low service life, poor conductivity and the like, and cannot meet the application requirements.
Disclosure of Invention
The invention aims to provide a preparation method of a DSA electrode with a titanium dioxide coating on the surface, wherein the titanium dioxide coating prepared by the method has a microstructure with loose and porous surface layer and compact inner layer. Surface porous microstructure augmentation of Ti 4 O 7 The contact area of the electrode and the organic pollutant improves Ti 4 O 7 The electrode has the effect of degrading organic matters; the compact microstructure of the inner layer avoids the corrosion to the matrix in the electrolysis process and prolongs the service life of the electrode.
In order to achieve the above purpose, the technical scheme adopted by the invention is as follows:
a method for preparing a DSA electrode coated with a titanium suboxide coating, the method comprising the steps of:
(1) Cleaning the surface of the electrode titanium substrate processed into the required shape;
(2) Placing a titanium substrate in a stainless steel container filled with micro-arc oxidation electrolyte for micro-arc oxidation, and preparing a micro-arc oxidation coating on the surface of the titanium substrate;
(3) Washing and drying the micro-arc oxidation coating, then calcining in a muffle furnace to convert amorphous titanium oxide and anatase titanium oxide in the coating into rutile titanium dioxide, and then cooling along with the furnace to prepare the rutile titanium dioxide coating on a titanium substrate;
(4) Coating a reducing solution on the surface of the rutile titanium dioxide coating obtained in the step (3), and then drying to enable the reducing agent with a certain thickness to be attached to the surface of the coating;
(5) Calcining the titanium dioxide coating covered with the reducing agent in an atmosphere furnace, introducing mixed gas of hydrogen and nitrogen into the furnace in the calcining process, firstly cracking the reducing agent to form amorphous carbon, converting rutile titanium dioxide in the coating into titanium dioxide in a high-temperature environment, and cooling along with the furnace to obtain the DSA electrode with the titanium dioxide coating on the surface.
In the step (2), the micro-arc oxidation electrolyte is obtained by adding a powder additive, a dispersing agent and a surfactant into a basic electrolyte; the composition of the basic electrolyte is as follows: 0-5g/L of sodium hydroxide, 8-25 g/L of silicate, 2-10 g/L of phosphoric acid and/or phosphate, 0-10 g/L of boric acid and/or borate and the balance of water.
In the micro-arc oxidation electrolyte, the concentration of a powder additive is 3-15 g/L, the concentration of a dispersing agent is 0.2-2 g/L, and the concentration of a surfactant is 10-200 mg/L; the pH value of the micro-arc oxidation electrolyte is 9-11.
The powder additive is one or two of rutile titanium dioxide nano powder and magnesium oxide nano powder, and the particle size of the powder additive is 50-200nm; the dispersing agent is one or more of tetramethylammonium hydroxide, polyethylene glycol, polyethyleneimine, polyacrylic acid-acrylic ester and polymaleic acid-acrylic acid; the surfactant is one or more of sodium carboxymethyl cellulose, alkyl quaternary ammonium salt, cetyl trimethyl ammonium bromide, sodium dodecyl sulfate, didecyl dimethyl ammonium chloride, lignin sulfonate and modified lignin sulfonate.
In the step (2), the micro-arc oxidation applies bipolar pulse voltage by using a pulse power supply, wherein: the pulse frequency is 100-2000 Hz, the positive voltage amplitude is 350-500V, the negative voltage amplitude is 50-200V, the positive duty ratio is 10% -50%, and the negative duty ratio is 10% -50%; the current density of the oxidation reaction is controlled to be 0.5-5A/dm by a pulse power supply 2 The time of the oxidation reaction is 30-180 min.
In the step (3), the calcination temperature of the micro-arc oxidation coating in a muffle furnace is 700-900 ℃, and the calcination time is 2-3 h.
In the step (4), the reducing solution is obtained by mixing a reducing agent with water, and then heating and melting the mixture; the reducing agent is one or more of maleic acid, stearic acid and citric acid; the reducing solution is coated on the surface of the rutile titanium dioxide coating in a spray coating or dip coating mode, and the amount of the surface reducing agent can be increased in a multiple coating mode; and then drying in a drying box at the drying temperature of 130-150 ℃.
In the step (5), in the mixed gas of hydrogen and nitrogen, the volume ratio of the hydrogen to the nitrogen is 0.02-0.1, and the inlet flow rate of the mixed gas is (0.1-1) multiplied by the volume/min of the furnace body; in the calcination process, the temperature is 900-1100 ℃, the temperature rising rate is 2-10 ℃, and the reduction time is 2-3 h.
In the step (5), the thickness of the titanium dioxide coating on the surface of the DSA electrode is 5-100 micrometers.
Compared with the prior art, the invention has the following beneficial technical effects:
1. the preparation method of the titanium-based titanium oxide DSA electrode adopts the micro-arc oxidation technology to prepare the oxide film layer on the titanium substrate, and the titanium oxide film layer is formed by calcining and reducing, so that the method is simple, the production efficiency is high, and the size of the product is not limited by the specification of a hot-pressing die;
2. in the preparation method adopted by the invention, the oxide film layer containing the nano titanium oxide and magnesium oxide seed crystal is prepared by a micro-arc oxidation technology. By adding nano rutile titanium oxide and magnesia powder, preferably a proper dispersing agent and surfactant, to the solution, the dispersibility of the powder is improved, and the powder carries positive charges. The bipolar pulse voltage is applied to regulate negative voltage to promote the adsorption of powder on the surface of the film, and the conversion of micro-arc eruption intensity and sintering intensity is controlled to control the growth process of the film, so that more nano titanium oxide and magnesium oxide are arranged in the film. The nano-crystal seeds can be used as nano-crystal seeds to reduce the temperature required by the crystal transformation of rutile in the process of transforming the film layer into rutile, and the grain size of the rutile can be reduced by low-temperature sintering, so that the phenomenon that the coating falls off due to the fact that the excessive growth of crystal grains and the excessive difference of the thermal expansion coefficients of the coating and a matrix in the preparation of titanium dioxide are avoided. In addition, the rutile grain refinement can also reduce the reduction temperature of titanium dioxide and realize low-temperature reduction.
3. According to the preparation method, organic matters are firstly cracked to form amorphous carbon, the rutile titanium dioxide coating is quantitatively reduced to prepare the titanium dioxide coating, and carbon can permeate into holes during cracking in a spraying mode of soluble organic matters, so that the reduction efficiency is improved, the reduction temperature is reduced, and low-temperature reduction is realized. Meanwhile, the reducing agent content is controlled by the spraying times, so that the reduction degree is controlled, avoiding excessive reduction of titanium oxide, and ensuring that the coating contains more Ti as much as possible 4 O 7 The coating has higher conductivity.
4. The titanium dioxide coating prepared by the invention has a microstructure structure with loose and porous surface layer and compact inner layer. Surface porous structure enlargement Ti 4 O 7 The contact area of the electrode and the organic pollutant improves Ti 4 O 7 The electrode has the effect of degrading organic matters; the compact microstructure of the inner layer avoids the corrosion to the matrix in the electrolysis process and prolongs the service life of the electrode.
Drawings
FIG. 1 is an X-ray diffraction pattern of the titanium dioxide coating prepared in example 1.
FIG. 2 is a graph of oxygen consumption versus treatment time for degradation of phenol by a titanium dioxide coated DSA electrode prepared in example 1.
Detailed Description
The present invention will be described in further detail with reference to specific examples.
The invention provides a preparation method of a DSA electrode coated with a titanium dioxide coating on the surface, which takes titanium as a carrier, adopts a micro-arc oxidation method to prepare a porous oxide film layer on the surface and a compact oxide film layer on the inner layer, then calcines the film layer to be converted into a rutile titanium dioxide coating, and then reduces to form the titanium dioxide coating, thus preparing the electrode.
Preferably, the titanium substrate is selected from a titanium plate, a titanium mesh or porous titanium.
Example 1:
test piece material: ta0 titanium alloy plate, dimensions 100mm by 2mm.
The preparation method comprises the following steps:
1. the titanium plate is put into a metal degreasing agent (composition: 5g/L of sodium hydroxide, 20g/L of sodium phosphate, 20g/L of sodium carbonate, 0.1g/L of OP-10 and the balance of water), ultrasonically cleaned for 10min at 90 ℃, and then put into deionized water, and ultrasonically cleaned for 10min at 90 ℃.
2. Drying the moisture on the surface of the titanium plate by adopting compressed air, and putting the titanium plate into the micro-arc oxidation electrolyte. The surface of the titanium sheet is placed in electrolyte to serve as an anode, and stainless steel is placed in the electrolyte to serve as a cathode. The micro-arc oxidation electrolyte is obtained by adding a powder additive, a dispersing agent and a surfactant into a basic electrolyte; the basic electrolyte comprises the following components: 10g/L of sodium silicate, 5g/L of sodium pyrophosphate, 1g/L of phosphoric acid and the balance of water; the concentration of the powder additive in the micro-arc oxidation electrolyte is as follows: 5g/L of nano rutile titanium dioxide powder, wherein the diameter of the powder is 50-200nm; the concentration of the dispersing agent in the micro-arc oxidation electrolyte is as follows: polyethylene glycol dispersant 1g/L; the concentration of the surfactant in the micro-arc oxidation electrolyte is as follows: 50mg/L of sodium dodecyl sulfate and 50mg/L of sodium methylcellulose. The pH of the micro-arc oxidation electrolyte was 10. The square wave pulse voltage applied to the electrolytic loop by the high-power pulse power supply has the frequency of 500Hz, the positive voltage amplitude of 400V, the negative voltage amplitude of 100V and the duty ratio of: the forward duty cycle is 30%, the negative duty cycle is 10%. Current density 3A/dm 2 The oxidation time is 80min, and the temperature of the electrolyte is 25 ℃. The thickness of the micro-arc oxidation coating is 30-32 μm by using an eddy current thickness meter.
3. And calcining the prepared micro-arc oxidation coating in a muffle furnace at 700 ℃ for 2 hours, and cooling to room temperature along with the furnace to obtain the rutile titanium dioxide coating.
4. Spraying a reducing solution on the surface of the rutile titanium dioxide coating, wherein the reducing solution is a sticky liquid obtained by mixing a reducing agent maleic acid and water according to the mass ratio of 100:50, heating to 95 ℃ and dissolving, and rapidly transferring the solution to a drying box at 130 ℃ after the solution is sprayed to a state that the surface is almost flowing until the surface is dry. The spraying was repeated 2 times.
5. Calcining the sample prepared in the previous step in an atmosphere furnace of a 5L furnace body, and introducing mixed gas of hydrogen and nitrogen into the atmosphere furnace, wherein the volume ratio of the hydrogen to the nitrogen is 0.02, and the flow rate of the mixed gas is 0.5L/min. The atmosphere furnace is gradually heated to 1000 ℃ according to the heating rate of 5 ℃/min, the temperature is kept at 1000 ℃ for 2 hours, the reducing agent is firstly cracked to form amorphous carbon which is attached to the inside of the porous layer of the coating, and rutile titanium dioxide in the coating is reduced to titanium dioxide in the high-temperature chamber. And cooling the titanium plate sample along with the furnace to obtain the DSA electrode coated with the titanium dioxide coating.
Analysis of the coating composition by X-ray diffraction, as shown in FIG. 1, shows that the major phase composition of the coating is Ti 4 O 7 . The thickness of the metallographic observation film layer is consistent with that of the original micro-arc oxidation film layer, and the thickness of the original micro-arc oxidation film is not changed after reduction. In simulating the effect of an organic wastewater test electrode, the concentrations of phenol and sodium sulfate in the wastewater were 90mg/L and 14.2g/L, respectively, with a total volume of 5 liters. The current density during electrochemical oxidation was 1.5mA/cm 2 The chemical oxygen consumption of the simulated organic wastewater is tested every 0.5 h. The chemical oxygen consumption corresponds to the organic matter content in the simulated organic wastewater, the time-dependent change curve of the simulated organic wastewater chemical oxygen consumption is shown in figure 2, the initial chemical oxygen consumption of the simulated organic wastewater is 210mg/L, the chemical oxygen consumption of the simulated organic wastewater after electrochemical oxidation of 3h is 23mg/L, the chemical oxygen consumption removal rate is 89%, and the prepared titanium-based titanium oxide electrode has higher electrochemical oxidation activity.
Example 2:
test piece material: ta0 titanium alloy net, size 100mm x 2mm, mesh 10mm x 15mm.
The preparation method comprises the following steps:
1. the titanium mesh was put into a metal degreasing agent (same as in example 1), ultrasonically cleaned at 90 ℃ for 10min, and then put into deionized water, ultrasonically cleaned at 90 ℃ for 10min.
2. Drying the water on the surface of the titanium mesh by adopting compressed air, and putting the titanium mesh into the micro-arc oxidation electrolyte. The surface of the titanium sheet is placed in electrolyte to serve as an anode, and stainless steel is placed in the electrolyte to serve as a cathode. Micro-scaleThe arc oxidation is obtained by adding a powder additive, a dispersing agent and a surfactant into a basic electrolyte; the basic electrolyte comprises the following components: 10g/L of sodium silicate, 5g/L of sodium phosphate, 3g/L of sodium borate and the balance of water; the concentration of the powder additive in the micro-arc oxidation electrolyte is as follows: the nano rutile titanium dioxide powder is 8g/L, and the diameter of the powder is 50-200nm; the concentration of the dispersing agent in the micro-arc oxidation electrolyte is as follows: polyethylene glycol dispersant 1.2g/L; the concentration of the surfactant in the micro-arc oxidation electrolyte is as follows: 30mg/L sodium dodecyl sulfate and 70mg/L sodium methylcellulose; the pH of the micro-arc oxidation electrolyte was 11. The square wave pulse voltage applied to the electrolytic loop by the high-power pulse power supply has the frequency of 500Hz, the positive voltage amplitude of 450V, the negative voltage amplitude of 120V and the duty ratio of: the positive duty cycle is 30% and the negative duty cycle is 20%. Current density 3A/dm 2 The oxidation time is 120min, and the temperature of the electrolyte is 25 ℃. The thickness of the micro-arc oxidation coating is measured to be 50-60 mu m by an eddy current thickness meter.
3. Calcining the micro-arc oxidation coating prepared in the last step in a muffle furnace at 650 ℃ for 2 hours, and then cooling to room temperature along with the furnace to obtain the rutile titanium dioxide coating.
4. Spraying a reducing solution on the surface of the rutile titanium dioxide coating, wherein the reducing solution is prepared by mixing maleic acid, citric acid and water according to a ratio of 100: the thick liquid obtained by mixing and heating to 95 ℃ for dissolution in a mass ratio of 50:100 is sprayed to a state that the surface is nearly flowing, and then the mixture is quickly transferred to a drying box at 130 ℃ until the surface is dry. The spraying was repeated 5 times.
5. Calcining the sample prepared in the previous step in an atmosphere furnace with the volume of a 5L furnace body, introducing mixed gas of hydrogen and nitrogen into the atmosphere furnace, wherein the volume ratio of the hydrogen to the nitrogen is 0.02, and the flow rate of the mixed gas is 0.5L/min. The atmosphere furnace is gradually heated to 1000 ℃ according to the heating rate of 5 ℃/min, and is kept at 1000 ℃ for 3 hours, and the reducing agent is firstly cracked to form amorphous carbon which is attached to the coating, so that rutile titanium dioxide in the coating is reduced to titanium dioxide. And then cooling the sample along with the furnace to obtain the DSA electrode coated with the titanium dioxide coating.
Analysis of coating phase composition Using X-ray diffraction of primary Ti 4 O 7 And a small amount of Ti 3 O 5 Indicating that there is some overdriving. The effect of the electrode is tested in simulating organic wastewater. The concentrations of phenol and sodium sulfate were 90mg/L and 14.2g/L, respectively, with a total volume of 5 liters. The current density during electrochemical oxidation was 1.5mA/cm 2 The chemical oxygen consumption of the simulated organic wastewater is tested every 0.5 h. The initial chemical oxygen consumption of the simulated organic wastewater is 210mg/L, the chemical oxygen consumption of the simulated organic wastewater after electrochemical oxidation of 3h is 32mg/L, the chemical oxygen consumption removal rate is 84.7%, and the prepared titanium-based titanium oxide electrode has higher electrochemical oxidation activity.
Example 3:
test piece material: ta0 titanium alloy plate, dimensions 100mm by 2mm,
the preparation method comprises the following steps:
1. the titanium plate was put into a metal degreasing agent (same as in example 1), ultrasonically cleaned at 90 ℃ for 10min, and then put into deionized water, ultrasonically cleaned at 90 ℃ for 10min.
2. Drying the moisture on the surface of the titanium plate by adopting compressed air, and putting the titanium plate into the micro-arc oxidation electrolyte. The surface of the titanium sheet is placed in electrolyte to serve as an anode, and stainless steel is placed in the electrolyte to serve as a cathode. The micro-arc oxidation electrolyte is obtained by adding a powder additive, a dispersing agent and a surfactant into a basic electrolyte; the basic electrolyte comprises the following components: 10g/L of sodium silicate, 5g/L of sodium phosphate, 2g/L of boric acid and the balance of water; the concentration of the powder additive in the micro-arc oxidation electrolyte is as follows: 5g/L of nano rutile titanium dioxide powder, 5g/L of nano magnesium oxide and 50-200nm of powder diameter; the concentration of the dispersing agent in the micro-arc oxidation electrolyte is as follows: polyethylene glycol dispersant 1g/L, polyacrylic acid-acrylic ester 1g/L; the concentration of the surfactant in the micro-arc oxidation electrolyte is as follows: 50mg/L of sodium dodecyl sulfate and 50mg/L of sodium methylcellulose. The pH of the micro-arc oxidation electrolyte was 9.8. The square wave pulse voltage applied to the electrolytic loop by the high-power pulse power supply has the frequency of 1000Hz, the positive voltage amplitude of 350V, the negative voltage amplitude of 80V and the duty ratio of: the positive duty cycle is 30% and the negative duty cycle is 10%. Current density 3A/dm 2 The oxidation time is 30min, and the temperature of the electrolyte is 25 ℃. The thickness of the micro-arc oxidation coating is 10-13 μm by using an eddy current thickness meter.
3. And calcining the prepared micro-arc oxidation coating in a muffle furnace at the temperature of 650 ℃ for 2 hours, and then cooling to room temperature along with the furnace to obtain the rutile titanium dioxide coating.
4. Spraying a reducing solution on the surface of the rutile titanium dioxide coating, wherein the reducing solution is a relatively viscous liquid obtained by mixing a reducing agent maleic acid and water according to the mass ratio of 100:50 and then heating to 95 ℃ for dissolution, and rapidly transferring the mixture to a drying box at 130 ℃ after the mixture is sprayed to a state that the surface is nearly flowing until the surface is dry. Spraying for 1 time.
5. Calcining the sample prepared in the previous step in an atmosphere furnace with the volume of a 5L furnace body, introducing mixed gas of hydrogen and nitrogen into the atmosphere furnace, wherein the volume ratio of the hydrogen to the nitrogen is 0.02, and the flow rate of the mixed gas is 0.5L/min. The atmosphere furnace is gradually heated to 970 ℃ according to the heating rate of 5 ℃/min, and is kept at 970 ℃ for 1.5h, and the reducing agent is firstly cracked to form amorphous carbon which is attached to the coating, so that rutile titanium dioxide in the coating is reduced to titanium dioxide. And then cooling the sample along with the furnace to obtain the DSA electrode coated with the titanium dioxide coating.
The phase composition of the coating is mainly Ti by X-ray diffraction analysis 4 O 7 . Phenol and sodium sulfate are dissolved in water to prepare simulated organic wastewater, and the effect of the electrode is tested. The concentrations of phenol and sodium sulfate were 90mg/L and 14.2g/L, respectively, with a total volume of 5 liters. The current density during electrochemical oxidation was 1.5mA/cm 2 The chemical oxygen consumption of the simulated organic wastewater is tested every 0.5 h. The initial chemical oxygen consumption of the simulated organic wastewater is 210mg/L, the chemical oxygen consumption of the simulated organic wastewater after electrochemical oxidation of 3h is 37mg/L, and the chemical oxygen consumption removal rate is 82.4%, which shows that the prepared titanium-based titanium oxide electrode has higher electrochemical oxidation activity.
Finally, it should be noted that: the above embodiments are only for illustrating the technical solution of the present invention, and not for limiting the same; although the invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical scheme described in the foregoing embodiments can be modified or some or all of the technical features thereof can be replaced by equivalents; such modifications and substitutions do not depart from the spirit of the invention.
Claims (5)
1. A preparation method of a DSA electrode with a titanium dioxide coating on the surface is characterized by comprising the following steps: the method comprises the following steps:
(1) Cleaning the surface of the electrode titanium substrate processed into the required shape;
(2) Placing a titanium substrate in a stainless steel container filled with micro-arc oxidation electrolyte for micro-arc oxidation, and preparing a micro-arc oxidation coating on the surface of the titanium substrate;
(3) Washing and drying the micro-arc oxidation coating, then calcining in a muffle furnace to convert amorphous titanium oxide and anatase titanium oxide in the coating into rutile titanium dioxide, and then cooling along with the furnace to prepare the rutile titanium dioxide coating on a titanium substrate;
(4) Coating a reducing solution on the surface of the rutile titanium dioxide coating obtained in the step (3), and then drying to enable the reducing agent with a certain thickness to be attached to the surface of the coating;
(5) Calcining the titanium dioxide coating covered with the reducing agent in an atmosphere furnace, introducing mixed gas of hydrogen and nitrogen into the furnace in the calcining process, firstly cracking the reducing agent into carbon, reducing rutile titanium dioxide to convert the rutile titanium dioxide into titanium dioxide, and cooling the titanium dioxide along with the furnace to obtain the DSA electrode with the titanium dioxide coating on the surface;
in the step (2), the micro-arc oxidation electrolyte is obtained by adding a powder additive, a dispersing agent and a surfactant into a basic electrolyte; the powder additive is rutile titanium dioxide nano powder or a mixture of rutile titanium dioxide nano powder and magnesium oxide nano powder, and the particle size of the powder additive is 50-200nm; the dispersing agent is one or more of tetramethylammonium hydroxide, polyethylene glycol, polyethyleneimine, polyacrylic acid-acrylic ester and polymaleic acid-acrylic acid; the surfactant is one or more of sodium carboxymethyl cellulose, alkyl quaternary ammonium salt, cetyl trimethyl ammonium bromide, sodium dodecyl sulfate, didecyl dimethyl ammonium chloride, lignin sulfonate and modified lignin sulfonate;
in the step (2), the micro-arc oxidation applies bipolar pulse voltage by adopting a pulse power supply, wherein: the pulse frequency is 100-2000 Hz, the positive voltage amplitude is 350-500V, the negative voltage amplitude is 50-200V, the positive duty ratio is 10% -50%, and the negative duty ratio is 10% -50%; the current density of the oxidation reaction is controlled to be 0.5-5A/dm by a pulse power supply 2 The time of the oxidation reaction is 30-180 min;
in the step (3), the calcination temperature of the micro-arc oxidation coating in a muffle furnace is 700-900 ℃, and the calcination time is 2-3 h;
in the step (4), the reducing solution is obtained by mixing a reducing agent with water and then heating and dissolving the mixture; the reducing agent is one or more of maleic acid, stearic acid and citric acid; the reducing solution is coated on the surface of the rutile titanium dioxide coating in a spray coating or dip coating mode, and the amount of the surface reducing agent can be increased in a multiple coating mode; then drying is carried out in a drying box, and the drying temperature is 130-150 ℃;
in the step (5), the temperature is 900-1100 ℃, the temperature rising rate is 2-10 ℃ and the reduction time is 2-3 h in the calcination process.
2. The method for producing a DSA electrode coated with a titanium suboxide coating according to claim 1, wherein: the composition of the basic electrolyte is as follows: 0-5g/L of sodium hydroxide, 8-25 g/L of silicate, 2-10 g/L of phosphoric acid and/or phosphate, 0-10 g/L of boric acid and/or borate and the balance of water.
3. The method for producing a DSA electrode coated with a titanium suboxide coating according to claim 1 or 2, characterized by: in the micro-arc oxidation electrolyte, the concentration of a powder additive is 3-15 g/L, the concentration of a dispersing agent is 0.2-2 g/L, and the concentration of a surfactant is 10-200 mg/L; the pH value of the micro-arc oxidation electrolyte is 9-11.
4. The method for producing a DSA electrode coated with a titanium-based titanium oxide coating layer according to claim 1, characterized in that: in the step (5), in the mixed gas of the hydrogen and the nitrogen, the volume ratio of the hydrogen to the nitrogen is 0.02-0.1, and the inlet flow rate of the mixed gas is (0.1-1) multiplied by the volume/min of the furnace body.
5. The method for producing a titanium-oxide-coated DSA electrode according to claim 1, characterized in that: in the step (5), the thickness of the titanium dioxide coating on the surface of the DSA electrode is 5-100 micrometers.
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| JPH04342420A (en) * | 1991-05-16 | 1992-11-27 | Toho Titanium Co Ltd | Production of titanium suboxide |
| CA2450978A1 (en) * | 2001-11-22 | 2003-06-05 | Francois Cardarelli | A method for electrowinning of titanium metal or alloy from titanium oxide containing compound in the liquid state |
| CN105734642A (en) * | 2016-03-29 | 2016-07-06 | 上海博友金属制品有限公司 | Preparing method for high-strength and large-specific-surface-area titanium black coating |
| CN109701510A (en) * | 2019-01-28 | 2019-05-03 | 广东朗研科技有限公司 | A kind of preparation method of Magneli phase oxidation titanium mesopore surfaces |
| CN110071302A (en) * | 2019-04-26 | 2019-07-30 | 西安理工大学 | A kind of titanium-based Asia titanium oxide bipolar plates and preparation method thereof |
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH04342420A (en) * | 1991-05-16 | 1992-11-27 | Toho Titanium Co Ltd | Production of titanium suboxide |
| CA2450978A1 (en) * | 2001-11-22 | 2003-06-05 | Francois Cardarelli | A method for electrowinning of titanium metal or alloy from titanium oxide containing compound in the liquid state |
| CN105734642A (en) * | 2016-03-29 | 2016-07-06 | 上海博友金属制品有限公司 | Preparing method for high-strength and large-specific-surface-area titanium black coating |
| CN109701510A (en) * | 2019-01-28 | 2019-05-03 | 广东朗研科技有限公司 | A kind of preparation method of Magneli phase oxidation titanium mesopore surfaces |
| CN110071302A (en) * | 2019-04-26 | 2019-07-30 | 西安理工大学 | A kind of titanium-based Asia titanium oxide bipolar plates and preparation method thereof |
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