CN116573728B - Preparation method of titanium anode plate for water treatment - Google Patents
Preparation method of titanium anode plate for water treatment Download PDFInfo
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- CN116573728B CN116573728B CN202310655911.7A CN202310655911A CN116573728B CN 116573728 B CN116573728 B CN 116573728B CN 202310655911 A CN202310655911 A CN 202310655911A CN 116573728 B CN116573728 B CN 116573728B
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- 239000010936 titanium Substances 0.000 title claims abstract description 163
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 title claims abstract description 149
- 229910052719 titanium Inorganic materials 0.000 title claims abstract description 149
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 32
- 238000002360 preparation method Methods 0.000 title claims description 28
- 239000000758 substrate Substances 0.000 claims abstract description 107
- 230000003647 oxidation Effects 0.000 claims abstract description 72
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 72
- 238000000034 method Methods 0.000 claims abstract description 48
- XOLBLPGZBRYERU-UHFFFAOYSA-N SnO2 Inorganic materials O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 claims abstract description 27
- 229910010413 TiO 2 Inorganic materials 0.000 claims abstract description 24
- GVFOJDIFWSDNOY-UHFFFAOYSA-N antimony tin Chemical compound [Sn].[Sb] GVFOJDIFWSDNOY-UHFFFAOYSA-N 0.000 claims abstract description 18
- 229910006404 SnO 2 Inorganic materials 0.000 claims abstract description 16
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Inorganic materials O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 claims abstract description 14
- YEAUATLBSVJFOY-UHFFFAOYSA-N tetraantimony hexaoxide Chemical compound O1[Sb](O2)O[Sb]3O[Sb]1O[Sb]2O3 YEAUATLBSVJFOY-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000000243 solution Substances 0.000 claims description 60
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 40
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 21
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 21
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical class OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 20
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 18
- 238000010438 heat treatment Methods 0.000 claims description 17
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 16
- 238000004140 cleaning Methods 0.000 claims description 16
- 239000007788 liquid Substances 0.000 claims description 16
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 15
- 238000001816 cooling Methods 0.000 claims description 15
- 238000001035 drying Methods 0.000 claims description 15
- 238000004070 electrodeposition Methods 0.000 claims description 15
- MIMUSZHMZBJBPO-UHFFFAOYSA-N 6-methoxy-8-nitroquinoline Chemical compound N1=CC=CC2=CC(OC)=CC([N+]([O-])=O)=C21 MIMUSZHMZBJBPO-UHFFFAOYSA-N 0.000 claims description 14
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 14
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 13
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 11
- 239000002904 solvent Substances 0.000 claims description 11
- SATCULPHIDQDRE-UHFFFAOYSA-N piperonal Chemical compound O=CC1=CC=C2OCOC2=C1 SATCULPHIDQDRE-UHFFFAOYSA-N 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 10
- 239000012046 mixed solvent Substances 0.000 claims description 9
- 238000004506 ultrasonic cleaning Methods 0.000 claims description 9
- 230000001590 oxidative effect Effects 0.000 claims description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 7
- 229910002804 graphite Inorganic materials 0.000 claims description 7
- 239000010439 graphite Substances 0.000 claims description 7
- 235000019441 ethanol Nutrition 0.000 claims description 6
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 claims description 5
- 239000007864 aqueous solution Substances 0.000 claims description 5
- DAMJCWMGELCIMI-UHFFFAOYSA-N benzyl n-(2-oxopyrrolidin-3-yl)carbamate Chemical compound C=1C=CC=CC=1COC(=O)NC1CCNC1=O DAMJCWMGELCIMI-UHFFFAOYSA-N 0.000 claims description 5
- 238000007664 blowing Methods 0.000 claims description 5
- 238000009835 boiling Methods 0.000 claims description 5
- TVQLLNFANZSCGY-UHFFFAOYSA-N disodium;dioxido(oxo)tin Chemical compound [Na+].[Na+].[O-][Sn]([O-])=O TVQLLNFANZSCGY-UHFFFAOYSA-N 0.000 claims description 5
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 5
- 229910021645 metal ion Inorganic materials 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- 235000006408 oxalic acid Nutrition 0.000 claims description 5
- 229940081310 piperonal Drugs 0.000 claims description 5
- 229910052707 ruthenium Inorganic materials 0.000 claims description 5
- -1 ruthenium ions Chemical class 0.000 claims description 5
- YBCAZPLXEGKKFM-UHFFFAOYSA-K ruthenium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Ru+3] YBCAZPLXEGKKFM-UHFFFAOYSA-K 0.000 claims description 5
- 238000005488 sandblasting Methods 0.000 claims description 5
- 238000002791 soaking Methods 0.000 claims description 5
- FQENQNTWSFEDLI-UHFFFAOYSA-J sodium diphosphate Chemical compound [Na+].[Na+].[Na+].[Na+].[O-]P([O-])(=O)OP([O-])([O-])=O FQENQNTWSFEDLI-UHFFFAOYSA-J 0.000 claims description 5
- 229940048086 sodium pyrophosphate Drugs 0.000 claims description 5
- 229940079864 sodium stannate Drugs 0.000 claims description 5
- 235000019818 tetrasodium diphosphate Nutrition 0.000 claims description 5
- 239000001577 tetrasodium phosphonato phosphate Substances 0.000 claims description 5
- 229910001432 tin ion Inorganic materials 0.000 claims description 5
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- 238000007605 air drying Methods 0.000 claims description 2
- 238000005530 etching Methods 0.000 claims description 2
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 claims description 2
- 239000002071 nanotube Substances 0.000 abstract description 13
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 abstract description 10
- XXLJGBGJDROPKW-UHFFFAOYSA-N antimony;oxotin Chemical compound [Sb].[Sn]=O XXLJGBGJDROPKW-UHFFFAOYSA-N 0.000 abstract description 10
- 230000000694 effects Effects 0.000 abstract description 9
- GYAUSKBLMWXBAV-UHFFFAOYSA-N oxotin;ruthenium Chemical compound [Ru].[Sn]=O GYAUSKBLMWXBAV-UHFFFAOYSA-N 0.000 abstract description 8
- 238000007654 immersion Methods 0.000 abstract description 7
- 239000006104 solid solution Substances 0.000 abstract description 7
- 238000004065 wastewater treatment Methods 0.000 abstract description 7
- 238000002161 passivation Methods 0.000 abstract description 6
- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(IV) oxide Inorganic materials O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 abstract description 6
- 238000011010 flushing procedure Methods 0.000 abstract description 5
- 239000013543 active substance Substances 0.000 abstract description 2
- 239000003792 electrolyte Substances 0.000 abstract description 2
- 239000002585 base Substances 0.000 abstract 2
- 239000002253 acid Substances 0.000 abstract 1
- 239000003513 alkali Substances 0.000 abstract 1
- 239000010410 layer Substances 0.000 description 125
- 230000000052 comparative effect Effects 0.000 description 17
- 239000002351 wastewater Substances 0.000 description 16
- 150000002500 ions Chemical class 0.000 description 15
- 239000011248 coating agent Substances 0.000 description 13
- 238000000576 coating method Methods 0.000 description 13
- 239000010865 sewage Substances 0.000 description 9
- 230000001681 protective effect Effects 0.000 description 6
- 238000009991 scouring Methods 0.000 description 6
- 238000003487 electrochemical reaction Methods 0.000 description 5
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- GHPGOEFPKIHBNM-UHFFFAOYSA-N antimony(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Sb+3].[Sb+3] GHPGOEFPKIHBNM-UHFFFAOYSA-N 0.000 description 4
- 238000009792 diffusion process Methods 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- 239000004408 titanium dioxide Substances 0.000 description 4
- WWSDBFDBPQHWAY-UHFFFAOYSA-N [Ti].[Sn].[Sb] Chemical compound [Ti].[Sn].[Sb] WWSDBFDBPQHWAY-UHFFFAOYSA-N 0.000 description 3
- 238000004090 dissolution Methods 0.000 description 3
- 230000002035 prolonged effect Effects 0.000 description 3
- 230000001105 regulatory effect Effects 0.000 description 3
- 238000003980 solgel method Methods 0.000 description 3
- 239000003115 supporting electrolyte Substances 0.000 description 3
- RLFWWDJHLFCNIJ-UHFFFAOYSA-N 4-aminoantipyrine Chemical compound CN1C(C)=C(N)C(=O)N1C1=CC=CC=C1 RLFWWDJHLFCNIJ-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 2
- 239000010405 anode material Substances 0.000 description 2
- FFBHFFJDDLITSX-UHFFFAOYSA-N benzyl N-[2-hydroxy-4-(3-oxomorpholin-4-yl)phenyl]carbamate Chemical compound OC1=C(NC(=O)OCC2=CC=CC=C2)C=CC(=C1)N1CCOCC1=O FFBHFFJDDLITSX-UHFFFAOYSA-N 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- 238000005868 electrolysis reaction Methods 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000004576 sand Substances 0.000 description 2
- 238000004088 simulation Methods 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 238000002798 spectrophotometry method Methods 0.000 description 2
- 229910001887 tin oxide Inorganic materials 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- 238000002835 absorbance Methods 0.000 description 1
- YJVBLROMQZEFPA-UHFFFAOYSA-L acid red 26 Chemical compound [Na+].[Na+].CC1=CC(C)=CC=C1N=NC1=C(O)C(S([O-])(=O)=O)=CC2=CC(S([O-])(=O)=O)=CC=C12 YJVBLROMQZEFPA-UHFFFAOYSA-L 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 1
- 229910000410 antimony oxide Inorganic materials 0.000 description 1
- FAPDDOBMIUGHIN-UHFFFAOYSA-K antimony trichloride Chemical compound Cl[Sb](Cl)Cl FAPDDOBMIUGHIN-UHFFFAOYSA-K 0.000 description 1
- 238000003491 array Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000004042 decolorization Methods 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 238000004043 dyeing Methods 0.000 description 1
- 238000003717 electrochemical co-deposition Methods 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 239000011229 interlayer Substances 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
- 239000011259 mixed solution Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- VTRUBDSFZJNXHI-UHFFFAOYSA-N oxoantimony Chemical compound [Sb]=O VTRUBDSFZJNXHI-UHFFFAOYSA-N 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000002957 persistent organic pollutant Substances 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 229910001925 ruthenium oxide Inorganic materials 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- WHRNULOCNSKMGB-UHFFFAOYSA-N tetrahydrofuran thf Chemical compound C1CCOC1.C1CCOC1 WHRNULOCNSKMGB-UHFFFAOYSA-N 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 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
- C02F1/46104—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
-
- 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
Landscapes
- 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)
- Electrodes For Compound Or Non-Metal Manufacture (AREA)
Abstract
The invention provides a titanium anode plate (Ti-TiO 2.TNTs-RuO2+SnO2-SnO2+Sb2O3) for water treatment, which is characterized in that a nanotube array (Ti.TNTs) base layer with TiO 2 as a main component is formed on a titanium substrate by an electrolytic oxidation method, an intermediate layer (RuO 2+SnO2) with ruthenium-tin oxide as a main component is prepared on the base layer by an immersion thermal oxidation method, and finally an active layer (SnO 2+Sb2O3).TiO2 nanotube base layer can inhibit passivation of the titanium substrate) with tin-antimony oxide as a main component is prepared on the intermediate layer by an electrochemical codeposition and high-temperature oxidation method, the intermediate layer of ruthenium-tin oxide can improve electrochemical performance and electrocatalytic stability of the titanium anode plate, can effectively prevent permeation of oxidation active substances and electrolyte, and the tin-antimony active layer prepared by the electrochemical codeposition method has more electrocatalytic activity points, can form solid solution among the layers and has high binding force, so that the titanium anode plate for water treatment has excellent electrochemical activity and service life, high wastewater treatment capacity and acid and alkali flushing resistance.
Description
Technical Field
The invention belongs to the technical field of electrochemistry, relates to a preparation method of an anode material, and particularly relates to a preparation method of a titanium anode plate for water treatment.
Background
Along with the rapid development of industry, the discharge amount of wastewater is increased, the components of the wastewater tend to be complicated, and meanwhile, the discharge standard is improved, so that the efficient water wastewater treatment method is becoming more and more important. The electrochemical wastewater treatment technology adopting the DSA electrode (titanium-based active oxide coating electrode) has the advantages of strong oxidation property without adding a strong oxidant, no secondary pollution in the treatment process, capability of efficiently treating toxic, high-concentration and difficult-to-degrade wastewater and the like, and is widely concerned.
The electrode is the most critical factor influencing the wastewater treatment effect, and the performance of the anode material of the DSA electrode determines the development of the electrochemical wastewater treatment technology, and the electrode has the characteristics of corrosion resistance, high electrocatalytic activity, long service life and the like. In sewage with complex components, passivation of a titanium anode, consumption of a coating and falling off can lead to the inactivation of the anode, so that the service life of the DSA electrode is reduced. The passivation of the titanium anode is that active oxygen generated by the anode diffuses to the titanium substrate, and a passivation film is formed on the surface of the substrate, so that the structure between the substrate and the coating is damaged, the conductivity is reduced, and the coating is required to have good compactness; the consumption of the coating is that the metal oxide coating of the titanium anode participates in the direct oxidation process, which requires good electrochemical stability of the coating in addition to efficient activation performance; the coating is shed by long-time scouring of sewage to the titanium anode plate, so that the coating is shed or stripped, and the titanium anode is required to have good anti-scouring strength, and the titanium substrate and the coating are required to have good bonding capability.
The existing titanium anode plates are different in characteristics and cannot meet the requirements of the electrochemical wastewater treatment technology on the performance of the titanium anode plates.
Disclosure of Invention
Aiming at the requirements, the invention forms a nanotube array protection base layer of TiO 2 on a titanium substrate by an electrolytic oxidation method, prepares an intermediate layer containing ruthenium-tin oxide by a dipping thermal oxidation method, prepares an active layer of tin-antimony oxide by an electrochemical codeposition and high-temperature oxidation method, and provides a titanium anode plate Ti-TiO 2.TNTs-RuO2+SnO2-SnO2+Sb2O3 for water treatment, wherein the base layer, the intermediate layer and the active layer are sequentially prepared on the titanium substrate from inside to outside; the main component of the base layer is a nanotube array TiO 2 of TiO 2, the main component of the intermediate layer is RuO 2+SnO2 of ruthenium and tin oxide, and the main component of the active layer is SnO 2+Sb2O3 of tin and antimony oxide.
The preparation method of the titanium anode plate for water treatment comprises the following steps:
1. Pretreatment of a titanium substrate: performing surface sand blasting treatment on a titanium substrate, cleaning, then placing the titanium substrate into a sodium hydroxide solution with the concentration of 10% -20% at 60-90 ℃ for 1-2 hours to remove greasy dirt on the surface, taking out, cleaning, placing the titanium substrate into a slightly-boiling saturated oxalic acid solution for etching for 2-3 hours, and taking out the titanium substrate and placing the titanium substrate into a 1% -5% oxalic acid solution for later use after ultrasonic cleaning. The surface of the pretreated titanium substrate is clean and has no oxide layer, so that preparation is made for preparing a TiO 2 nano tube base layer which is arranged in a fine and orderly manner by subsequent electrolytic oxidation on the surface of the titanium substrate.
2. Preparation of a base layer: adding ammonium bifluoride NH 4HF2 and tetrahydrofuran THF into 70% -80% glycol aqueous solution, stirring uniformly to obtain electrolytic oxidation solution, in the electrolytic oxidation solution, washing the titanium substrate pretreated in the process 1, using graphite as a cathode, using the graphite as an anode, carrying out electrolytic oxidation for 35-45min at an electrolytic voltage of 17-22V, and placing the titanium substrate into absolute ethyl alcohol after the electrolytic oxidation is finished, and carrying out ultrasonic cleaning to obtain the titanium substrate with the TiO 2 TNTs base layer.
3. Preparation of an intermediate layer: dissolving the hydrated tin tetrachloride SnCl 4·5H2 O and the hydrated ruthenium trichloride RuCl 3·3H2 O in an alcohol solvent, slowly adding hydrochloric acid with the concentration of 10-15%, stirring and mixing uniformly to prepare a solution with the total metal ion concentration of 0.4-0.6 mol/L; soaking the titanium substrate obtained in the process 2 in the solution completely for 1-2min, taking out, blowing off superfluous surface liquid by a forced air drying mode, drying at 80-100 ℃ for 10-20min to evaporate the solvent, oxidizing at 450-500 ℃ for 10-15min in a muffle furnace, taking out the titanium substrate after the titanium substrate is completely cooled, soaking, drying and oxidizing at high temperature again, cooling, repeating the steps for 15-20 times, slowly heating to 450-500 ℃ in the muffle furnace for the last time, keeping the constant temperature for 1-1.5h, cooling to room temperature in the furnace, and taking out the titanium substrate with the RuO 2+SnO2 intermediate layer; the thickness of the intermediate layer can be gradually increased by repeated immersion and high-temperature oxidation, and in the repeated high-temperature oxidation process, the ion radius of Ru 4+ of the intermediate layer is similar to the ion radius of Ti 4+ of the base layer, so that solid solution can be gradually formed by mutual diffusion, and the bonding strength of the base layer and the intermediate layer is increased.
4. Preparation of active layer: ultrasonically cleaning the titanium substrate obtained in the process 3, taking the cleaned titanium substrate as a cathode, taking a SnO 2 base electrode as an anode, and electrodepositing in a tin-antimony electrodepositing solution at 25-30 ℃ for 50-70min at constant current density of 15-20mA/cm 2; and after the electrodeposition is finished, carrying out high-temperature thermal oxidation in a heating furnace, heating to 450-500 ℃ at a heating rate of 5-10 ℃/min, keeping the temperature for 2-2.5h, and increasing the bonding strength of the intermediate layer and the active layer besides forming a stable tin-antimony oxide active layer in the constant temperature process, cooling to room temperature slowly after keeping the temperature constant, and taking out to obtain the SnO 2+Sb2O3 active layer, thus obtaining the titanium anode plate for water treatment.
Preferably, in process 2: the mass percentage concentration of ammonium bifluoride in the electrolytic oxidation solution is 1% -2%, and the mass percentage concentration of tetrahydrofuran is 20% -25%; tetrahydrofuran can dissolve titanium substrate to form Ti 4+ ion, and is adsorbed on the surface of electrode under the action of tetrahydrofuran functional group, so that the titanium dioxide nanotube obtained by electrolytic oxidation is compact and ordered, and a small amount of ammonium bifluoride can raise the conductivity of electrolytic oxidation solution and raise the electrochemical reaction efficiency of the process.
Preferably, in process 3: the alcohol solvent is a mixed solvent of isopropyl alcohol and n-butanol with the same volume, the volume ratio of hydrochloric acid to the alcohol solvent is 1:15-20, and the molar mass ratio of ruthenium ions to tin ions in the solution is n (Ru 3+)：n(Sn4+) =3-4:10.
Preferably, in process 4: the tin-antimony electrodeposition liquid takes 10-14 parts of sodium stannate, 2-5 parts of antimony trichloride, 12-17 parts of citric acid, 3-5 parts of sodium pyrophosphate and 0.2-0.4 part of piperonal as main components, and the concentration of Sn 4+ in the tin-antimony electrodeposition liquid is 0.2-0.25mol/L.
The invention has the beneficial effects that:
1. The electrolytic oxidation method provided by the invention can form TiO 2 nano tubes which are orderly arranged perpendicular to the surface on the titanium substrate, the protective base layer structure is compact and orderly arranged, the mechanical strength of the titanium substrate can be enhanced, the passivation of the titanium substrate is inhibited, and the service life of the electrode can be effectively prolonged. The intermediate layer of the ruthenium tin oxide prepared by the immersion thermal oxidation method can not only reduce interface resistance, greatly improve electrochemical performance of the titanium anode plate, but also effectively prevent permeation of oxidation active substances and electrolyte, keep electrocatalytic stability and prolong service life of an electrode, and the ionic radius of Ru 4+ of the intermediate layer is similar to that of Ti 4+ of the base layer, so that the intermediate layer and the base layer are easily gradually diffused to form a solid solution in the multiple high-temperature oxidation process, so that the base layer and the intermediate layer can be mutually combined firmly, and the intermediate layer is resistant to sewage scouring, and the service life of the titanium anode is ensured.
2. The tin-antimony active layer prepared by the electrochemical codeposition and high-temperature oxidation method provided by the invention is denser, smoother and more in electrocatalytic activity points than that prepared by a sol-gel method and a thermal decomposition method. The high-temperature oxidation process after co-deposition can also enable the intermediate layer and the active layer to be mutually fused to form a solid solution crystalline phase structure, and because the intermediate layer and the active layer are both provided with SnO 2 oxide, the mutual fusion effect is better, the binding force is stronger, and the active layer is not easy to fall off even under the flushing of sewage during water treatment, so that the service life of the electrode can be greatly prolonged.
Detailed Description
Example 1:
The embodiment is a titanium anode plate Ti-TiO 2.TNTs-RuO2+SnO2-SnO2+Sb2O3 for water treatment prepared according to the content provided by the invention, and the preparation process and technological parameters are as follows:
1. Pretreatment of a titanium substrate: performing surface sand blasting treatment on a titanium substrate, cleaning, then placing the titanium substrate into a sodium hydroxide solution with the concentration of 20% at 90 ℃ for 2 hours to remove greasy dirt on the surface, taking out, cleaning, placing the titanium substrate into a slightly-boiling saturated oxalic acid solution to etch for 2.5 hours, and taking out the titanium substrate to be placed into a 1% oxalic acid solution for standby after ultrasonic cleaning; the surface of the pretreated titanium substrate is clean and has no oxide layer, so that preparation is made for preparing a TiO 2 nano tube base layer which is arranged in a fine and orderly manner by subsequent electrolytic oxidation on the surface of the titanium substrate.
2. Preparation of a base layer: adding ammonium bifluoride (NH 4HF2) and Tetrahydrofuran (THF) into an 80% glycol aqueous solution, uniformly stirring to prepare an electrolytic oxidation solution with the mass percent concentration of ammonium bifluoride being 2% and the mass percent concentration of tetrahydrofuran being 20%, washing a pretreated titanium substrate in the electrolytic oxidation solution to be used as an anode, taking graphite as a cathode, and carrying out electrolytic oxidation for 40min at the electrolytic voltage of 20V, wherein tetrahydrofuran in the electrolytic oxidation solution can dissolve the titanium substrate to form Ti 4+ ions, and the Ti 4+ ions are adsorbed on the surface of an electrode under the action of tetrahydrofuran functional groups, so that titanium dioxide nanotubes obtained by electrolytic oxidation are compact and orderly, the conductivity of the electrolytic oxidation solution can be improved by a small amount of ammonium bifluoride, the electrochemical reaction efficiency of the process is improved, and a titanium plate is put into absolute ethyl alcohol after the electrolytic oxidation is finished, and is cleaned by ultrasonic to obtain a titanium substrate with a TiO 2 TNT base layer;
3. preparation of an intermediate layer:
S1, dissolving hydrated tin tetrachloride (SnCl 4·5H2 O) and hydrated ruthenium trichloride (RuCl 3·3H2 O) in a mixed solvent with equal volume of isopropyl alcohol and n-butyl alcohol according to the molar mass ratio of ruthenium ions to tin ions in the solution of n (Ru 3+)：n(Sn4+) =3:10, slowly adding hydrochloric acid with the concentration of 15%, wherein the addition amount is one twentieth of the volume of the mixed solvent to promote the dissolution of metal salt, and stirring and mixing uniformly to prepare a solution with the concentration of total metal ions of 0.5 mol/L;
S2, fully immersing the titanium substrate containing the base layer in the solution obtained in the step S1, taking out the titanium substrate containing the base layer after 1min, blowing off superfluous liquid on the surface in a blast drying oven, drying at 100 ℃ for 10min to evaporate the solvent, oxidizing at 470 ℃ for 15min in a muffle furnace, taking out the titanium substrate after the titanium substrate is fully cooled, carrying out immersing, drying and high-temperature oxidation again, repeating the steps of cooling for 20 times, slowly heating to 470 ℃ in the muffle furnace for 1.5h at constant temperature for the last time, cooling to room temperature in the furnace, and taking out the titanium substrate with the base layer and the RuO 2+SnO2 intermediate layer; the thickness of the intermediate layer can be gradually increased by repeated immersion and high-temperature oxidation, and in the repeated high-temperature oxidation process, the ion radius of Ru 4+ of the intermediate layer is similar to the ion radius of Ti 4+ of the base layer, so that solid solution can be gradually formed by mutual diffusion, and the bonding strength of the base layer and the intermediate layer is increased.
4. Preparation of active layer:
S1, preparing a tin-antimony electrodeposition liquid with the concentration of Sn 4+ of 0.25mol/L by taking 12 parts of sodium stannate, 4 parts of antimony trichloride, 15 parts of citric acid, 4 parts of sodium pyrophosphate and 0.3 part of piperonal as main components of the tin-antimony electrodeposition liquid;
S2, ultrasonically cleaning a titanium substrate containing a base layer and an intermediate layer, taking the titanium substrate as a cathode, taking a SnO 2 base electrode as an anode, and electrodepositing the titanium substrate in the tin-antimony electrodepositing solution at a constant current density of 17mA/cm 2 and a temperature of 27 ℃ for 60min;
S3, performing high-temperature thermal oxidation in a resistance furnace after the electrodeposition is finished, heating to 470 ℃ at a heating rate of 5 ℃/min, keeping the temperature for 2.5 hours, and increasing the bonding strength of the intermediate layer and the active layer besides forming a stable tin-antimony oxide active layer in the constant temperature process, slowly cooling to room temperature after keeping the temperature constant, and taking out to obtain the SnO 2+Sb2O3 active layer, thereby obtaining the titanium anode plate for water treatment.
Example 2:
The embodiment is a titanium anode plate Ti-TiO 2.TNTs-RuO2+SnO2-SnO2+Sb2O3 for water treatment prepared according to the content provided by the invention, and the preparation process and technological parameters are as follows:
1. Pretreatment of a titanium substrate: performing surface sand blasting treatment on a titanium substrate, cleaning, then placing the titanium substrate into a sodium hydroxide solution with the concentration of 20% at 90 ℃ for 1 hour to remove greasy dirt on the surface, taking out, cleaning, placing the titanium substrate into a slightly-boiling saturated oxalic acid solution to etch for 2 hours, and taking out the titanium substrate and placing the titanium substrate into a 1% oxalic acid solution for standby after ultrasonic cleaning; the surface of the pretreated titanium substrate is clean and has no oxide layer, so that preparation is made for preparing a TiO 2 nano tube base layer which is arranged in a fine and orderly manner by subsequent electrolytic oxidation on the surface of the titanium substrate.
2. Preparation of a base layer: adding ammonium bifluoride (NH 4HF2) and Tetrahydrofuran (THF) into an 80% glycol aqueous solution, uniformly stirring to prepare an electrolytic oxidation solution with the mass percent concentration of the ammonium bifluoride being 1.5% and the mass percent concentration of the tetrahydrofuran being 23%, in the electrolytic oxidation solution, washing the titanium substrate pretreated in the process 1 clean and then taking the titanium substrate as an anode, taking graphite as a cathode, carrying out electrolytic oxidation for 45min at the electrolytic voltage of 17V, wherein the tetrahydrofuran can dissolve the titanium substrate to form Ti 4+ ions, and adsorbing the Ti 4+ ions on the surface of an electrode under the action of tetrahydrofuran functional groups, so that titanium dioxide nanotubes obtained by electrolytic oxidation are compact and orderly, the conductivity of the electrolytic oxidation solution can be improved by a small amount of ammonium bifluoride, the electrochemical reaction efficiency of the process is improved, and after the electrolytic oxidation is finished, putting a titanium plate into absolute ethyl alcohol, and carrying out ultrasonic cleaning to obtain the titanium substrate with a TiO 2 TNT base layer;
3. preparation of an intermediate layer:
S1, dissolving hydrated tin tetrachloride (SnCl 4·5H2 O) and hydrated ruthenium trichloride (RuCl 3·3H2 O) in a mixed solvent with equal volume of isopropyl alcohol and n-butyl alcohol according to the ratio of the molar mass ratio n (Ru 3+)：n(Sn4+) =3.5:10 of ruthenium ions to tin ions in the solution, slowly adding hydrochloric acid with the concentration of 15% to the mixed solvent, wherein the addition amount is one twentieth of the volume of the mixed solvent to promote the dissolution of metal salt, and uniformly stirring and mixing the mixed solution to prepare the solution with the concentration of 0.4mol/L of total metal ions;
S2, completely immersing the titanium substrate containing the base layer in the obtained solution, taking out the solution after 2min, blowing off superfluous liquid on the surface in a blast drying oven, drying at 100 ℃ for 15min to evaporate the solvent, oxidizing the solution at 500 ℃ for 10min in a muffle furnace, taking out the solution after the titanium substrate is completely cooled, carrying out the steps of immersing, drying, oxidizing at high temperature again, cooling for 15 times, slowly heating to 500 ℃ in the muffle furnace for 1h at constant temperature for the last time, cooling to room temperature in the furnace, and taking out the titanium substrate with the base layer and the RuO 2+SnO2 intermediate layer; the thickness of the intermediate layer can be gradually increased by repeated immersion and high-temperature oxidation, and in the repeated high-temperature oxidation process, the ion radius of Ru 4+ of the intermediate layer is similar to the ion radius of Ti 4+ of the base layer, so that solid solution can be gradually formed by mutual diffusion, and the bonding strength of the base layer and the intermediate layer is increased.
4. Preparation of active layer:
S1, preparing a tin-antimony electrodeposition liquid with the concentration of Sn 4+ of 0.2mol/L by taking 10 parts of sodium stannate, 5 parts of antimony trichloride, 12 parts of citric acid, 3 parts of sodium pyrophosphate and 0.2 part of piperonal as main components of the tin-antimony electrodeposition liquid;
S2, ultrasonically cleaning a titanium substrate containing a base layer and an intermediate layer, taking the titanium substrate as a cathode, taking a SnO 2 base electrode as an anode, and electrodepositing the titanium substrate in a tin-antimony electrodepositing solution at a temperature of 30 ℃ and a constant current density of 20mA/cm 2 for 70min;
S3, performing high-temperature thermal oxidation in a resistance furnace after the electrodeposition is finished, heating to 500 ℃ at a heating rate of 10 ℃/min, keeping the temperature for 2 hours, and in the constant temperature process, not only forming a stable tin-antimony oxide active layer, but also increasing the bonding strength of an intermediate layer and the active layer, cooling to room temperature slowly in the furnace after keeping the temperature constant, and taking out to obtain the SnO 2+Sb2O3 active layer, thereby obtaining the titanium anode plate for water treatment.
Example 3:
The embodiment is a titanium anode plate Ti-TiO 2.TNTs-RuO2+SnO2-SnO2+Sb2O3 for water treatment prepared according to the content provided by the invention, and the preparation process and technological parameters are as follows:
1. Pretreatment of a titanium substrate: performing surface sand blasting treatment on a titanium substrate, cleaning, then placing the titanium substrate into a sodium hydroxide solution with the concentration of 10% at 60 ℃ for 2 hours to remove greasy dirt on the surface, taking out, cleaning, placing the titanium substrate into a slightly-boiling saturated oxalic acid solution to etch for 3 hours, and taking out the titanium substrate and placing the titanium substrate into a 5% oxalic acid solution for standby after ultrasonic cleaning; the surface of the pretreated titanium substrate is clean and has no oxide layer, so that preparation is made for preparing a TiO 2 nano tube base layer which is arranged in a fine and orderly manner by subsequent electrolytic oxidation on the surface of the titanium substrate.
2. Preparation of a base layer: adding ammonium bifluoride (NH 4HF2) and Tetrahydrofuran (THF) into 70% glycol aqueous solution, uniformly stirring to prepare electrolytic oxidation solution with the mass percent concentration of ammonium bifluoride being 1% and the mass percent concentration of tetrahydrofuran being 25%, washing a pretreated titanium substrate in the electrolytic oxidation solution to be used as an anode, taking graphite as a cathode, and carrying out electrolytic oxidation for 35min at the electrolytic voltage of 22V, wherein tetrahydrofuran in the electrolytic oxidation solution can dissolve the titanium substrate to form Ti 4+ ions, and the Ti 4+ ions are adsorbed on the surface of an electrode under the action of tetrahydrofuran functional groups, so that titanium dioxide nanotubes obtained by electrolytic oxidation are compact and orderly, the conductivity of the electrolytic oxidation solution can be improved by a small amount of ammonium bifluoride, the electrochemical reaction efficiency of the process is improved, and after the electrolytic oxidation is finished, putting a titanium plate into absolute ethyl alcohol, and carrying out ultrasonic cleaning to obtain a titanium substrate with a TiO 2 TNT base layer;
3. preparation of an intermediate layer:
s1, dissolving hydrated tin tetrachloride (SnCl 4·5H2 O) and hydrated ruthenium trichloride (RuCl 3·3H2 O) in a mixed solvent with equal volume of isopropyl alcohol and n-butyl alcohol according to the molar mass ratio of ruthenium ions to tin ions in the solution of n (Ru 3+)：n(Sn4+) =4:10, slowly adding hydrochloric acid with the concentration of 10%, wherein the addition amount is one fifteenth of the volume of the mixed solvent to promote the dissolution of metal salt, and stirring and mixing uniformly to prepare a solution with the concentration of 0.6mol/L of total metal ions;
S2, fully immersing the titanium substrate containing the base layer in the solution obtained in the step S1, taking out the titanium substrate containing the base layer after 2min, blowing off superfluous liquid on the surface in a blast drying oven, drying at 80 ℃ for 20min to evaporate the solvent, oxidizing the titanium substrate at 450 ℃ for 15min in a muffle furnace, taking out the titanium substrate after the titanium substrate is fully cooled, carrying out immersing, drying and high-temperature oxidation again, repeating the steps of cooling for 18 times, slowly heating to 450 ℃ in the muffle furnace for 1.5h at constant temperature for the last time, cooling to room temperature in the furnace, and taking out the titanium substrate with the base layer and the RuO 2+SnO2 intermediate layer; the thickness of the intermediate layer can be gradually increased by repeated immersion and high-temperature oxidation, and in the repeated high-temperature oxidation process, the ion radius of Ru 4+ of the intermediate layer is similar to the ion radius of Ti 4+ of the base layer, so that solid solution can be gradually formed by mutual diffusion, and the bonding strength of the base layer and the intermediate layer is increased.
4. Preparation of active layer:
s1, preparing a tin-antimony electrodeposition liquid with the concentration of Sn 4+ of 0.25mol/L by taking 14 parts of sodium stannate, 2 parts of antimony trichloride, 17 parts of citric acid, 5 parts of sodium pyrophosphate and 0.4 part of piperonal as main components of the tin-antimony electrodeposition liquid;
S2, ultrasonically cleaning a titanium substrate containing a base layer and an intermediate layer, taking the titanium substrate as a cathode, taking a SnO 2 base electrode as an anode, and electrodepositing the titanium substrate in the tin-antimony electrodepositing solution at 25 ℃ for 50min at a constant current density of 15mA/cm 2;
S3, performing high-temperature thermal oxidation in a resistance furnace after the electrodeposition is finished, heating to 450 ℃ at the heating rate of 7 ℃/min, keeping the temperature for 2.5 hours, and increasing the bonding strength of the intermediate layer and the active layer besides forming a stable tin-antimony oxide active layer in the constant temperature process, slowly cooling to room temperature after keeping the temperature constant, and taking out to obtain the SnO 2+Sb2O3 active layer, thereby obtaining the titanium anode plate for water treatment.
Comparative example 1:
The water treatment titanium anode Ti-SnO 2+Sb2O3 prepared by sol-gel method is compared with the common tin-antimony-titanium anode, and the active layer of the water treatment titanium anode is mainly composed of oxides of tin and antimony.
SnCl 4、SbCl3, citric acid and ethylene glycol were formulated as n (metal salts): n (citric acid): n (ethylene glycol) =2:5:30 sol condensate, n (Sn 4+)：n(Sb3+) =25:2 in sol condensate. The titanium substrate is pretreated by the same method as in the embodiment 1, the sol condensate is coated on the pretreated titanium substrate, the titanium substrate is dried for 15min at 110 ℃, oxidized for 20min at 450 ℃ at high temperature in a muffle furnace, the coating, the drying and the high-temperature oxidation are repeated for 15 times, the temperature is slowly increased to 450 ℃ in the muffle furnace for 2h at high temperature oxidation, the furnace is cooled to room temperature, and the tin-antimony-titanium anode Ti-SnO 2+Sb2O3 prepared by the sol-gel method is obtained after being taken out. This comparative example is a common method of preparing tin antimony titanium anodes as a blank comparative example.
Comparative example 2:
The comparative example is to prepare an intermediate layer of ruthenium tin oxide directly on a Ti substrate as in example 1, and to continue to prepare an active layer of tin antimony oxide as in example 1, the titanium anode plate thus prepared is Ti-RuO 2+SnO2-SnO2+Sb2O3, a protective base layer free of nanotube arrays TiO 2. TNTs, for comparative illustration of the superiority of the TiO 2. TNTs base layer in the solution of the present application.
Comparative example 3:
In the comparative example, after preparing a protective base layer of TiO 2 and TNTs according to the method of example 1, preparing an active layer of tin-antimony oxide directly on the base layer according to the method of example 1, namely, the prepared titanium anode plate is Ti-TiO 2.TNTs-SnO2+Sb2O3, and does not contain an intermediate layer of ruthenium-tin oxide, which is used for comparing and explaining the superiority of the intermediate layer of ruthenium-tin oxide in the scheme of the application.
Comparative example 4:
this comparative example was prepared as in example 1, after the protective base layer of TNTs and the intermediate layer of ruthenium tin oxide, an active layer of tin antimony oxide was prepared on the intermediate layer as in comparative example 1, i.e., the titanium anode plate prepared was also Ti-TiO 2.TNTs-RuO2+SnO2-SnO2+Sb2O3, to compare the superiority of the "electrochemical co-deposition+high temperature oxidation" process for preparing an active layer of tin antimony oxide in the present application scheme.
The titanium anode plates obtained in the above examples and comparative examples were used as test pieces to test their electrocatalytic capacity for simulated sewage. Simulation treatment wastewater test device: in an electrolytic tank, a titanium plate is used as a cathode of an electrochemical reaction device, a titanium anode plate is used as an anode, the effective electrode area is 50mm multiplied by 50mm, the distance between the anode plate and the cathode plate is 3.5cm, 400ml of wastewater to be treated is added into the electrolytic tank, the pH value of the wastewater is regulated by using sulfuric acid and sodium hydroxide as an acid-base regulator, when the electrolysis is performed for 30min, 60min, 90min, 120min, 150min and 180min, a water sample is sampled and taken near the anode, the concentration of pollutants is measured, and the removal rate is calculated.
And (3) removing chromaticity of the simulated degradation printing and dyeing wastewater: the initial concentration of the acid scarlet simulated wastewater is 500mg/L, 10g/L of Na 2SO4 is added as supporting electrolyte, the pH of the wastewater is regulated to be neutral by an acid-base regulator, the optimal current density is set to 40mA/cm 2, water samples are taken at intervals, the absorbance is measured by an ultraviolet spectrophotometry, and the decolorization rate is calculated.
And (3) simulating and degrading COD in the wastewater: simulating the initial concentration of COD in the wastewater to be 500mg/L, adding 5g/L NaCl as a supporting electrolyte, regulating the PH of the wastewater to be 3 by using an acid-base regulator, setting the optimal current density to be 50mA/cm 2, taking water samples at intervals, measuring the content of COD Cr by using a rapid COD tester, and calculating the removal rate of the COD.
Simulation degradation phenol wastewater test: the method comprises the steps of adding 10g/L of Na 2SO4 serving as a supporting electrolyte into organic pollutants containing 200mg/L of phenol in the treated simulated wastewater, adjusting the pH of the wastewater to 10 by using an acid-base regulator, setting the optimal current density to be 30mA/cm 2, taking water samples at intervals for water quality analysis, measuring the phenol concentration by using a 4-aminoantipyrine spectrophotometry, and calculating the removal rate of the phenol.
The removal rates are shown in Table 1, and the results are the average values of the samples.
Table 1:
Electrode accelerated life test: the sample prepared was electrolyzed at a constant current of 40mA/cm 2 in a solution of H 2SO4 at 50℃and 1.0mol/L with a gap of 20mm between electrodes using a copper sheet as the cathode, and when the cell voltage was increased rapidly beyond the initial voltage by 10V, the electrolysis time at this time was the accelerated lifetime of the electrode, and the results are shown in Table 2.
Table 2:
And simulating an acid-base sewage scouring resistance test: weighing an anode plate sample, respectively soaking the sample in a 10% sulfuric acid solution at 40 ℃ and a 20% sodium hydroxide solution at 80 ℃ for 48 hours, flushing the surface of the sample in a circulating water tank at a water flow speed of 2m/S, adding fine sand particles into the circulating water to simulate impurities in sewage, taking out the test after flushing for 180 hours, cleaning the sand particles, drying the liquid, observing the surface coating condition of the anode plate, and weighing to calculate the weightlessness rate. The results are shown in Table 3.
Table 3:
As is clear from Table 1, each example had more excellent performance in simulating wastewater treatment and had higher electrocatalytic activity than each comparative example. As can be seen from example 1 compared with comparative example 2, tiO 2. The protective base layer of TNTs can inhibit passivation of the titanium substrate to a certain extent, and keep the activity of the titanium substrate; as can be seen from the comparison of example 1 and comparative example 3, the addition of the RuO 2+SnO2 intermediate layer by the immersion thermal oxidation method can effectively reduce the interface resistance and greatly increase the electrocatalytic performance; compared with comparative example 4, it is known that in the case of both the active layers of SnO 2+Sb2O3, the active layer of tin-antimony prepared by the method of electrochemical codeposition and high-temperature oxidation is denser, has more surface active points, has higher electrocatalytic activity and better removal rate of various indexes of the simulated wastewater.
As can be seen from Table 2, the addition of the TiO 2 TNT protective base layer and the RuO 2+SnO2 interlayer greatly prolonged the service life of the titanium anode without flushing.
As can be seen from Table 3, the base layer, the intermediate layer and the active layer of the titanium anode plate of each embodiment have strong bonding strength, the coating is not easy to fall off, and the titanium anode plate of each embodiment has better performance in the simulated acid-base sewage scouring resistance test than each comparative example, and has longer service life under the scouring of sewage during water treatment.
Claims (4)
1. The preparation method of the titanium anode plate for water treatment is characterized by comprising the following steps:
(1) Pretreatment of a titanium substrate: performing surface sand blasting treatment on a titanium substrate, cleaning, then placing the titanium substrate into a sodium hydroxide solution with the concentration of 10% -20% at 60-90 ℃ for 1-2 hours to remove greasy dirt on the surface, taking out, cleaning, placing the titanium substrate into a slightly boiling saturated oxalic acid solution for etching for 2-3 hours, and taking out the titanium substrate and placing the titanium substrate into a 1% -5% oxalic acid solution for standby after ultrasonic cleaning;
(2) Preparation of a base layer: adding ammonium bifluoride (NH 4HF2) and Tetrahydrofuran (THF) into 70% -80% glycol aqueous solution, stirring uniformly to obtain electrolytic oxidation solution, in the electrolytic oxidation solution, washing the titanium substrate pretreated in the process (1) cleanly, taking graphite as an anode, taking graphite as a cathode, carrying out electrolytic oxidation for 35-45min at 17-22V, putting the titanium plate into absolute ethyl alcohol after the electrolytic oxidation is finished, carrying out ultrasonic cleaning to obtain a titanium substrate with a TiO 2 TNTs base layer, and forming TiO 2 nano tubes which are arranged in order perpendicular to the surface on the titanium substrate;
(3) Preparation of an intermediate layer: dissolving hydrated stannic chloride (SnCl 4·5H2 O) and hydrated ruthenium trichloride (RuCl 3·3H2 O) in an alcohol solvent, slowly adding hydrochloric acid with the concentration of 10-15%, and uniformly stirring and mixing to prepare a solution with the total metal ion concentration of 0.4-0.6 mol/L; soaking the titanium substrate obtained in the process (2) in the solution completely for 1-2min, taking out, blowing off superfluous liquid on the surface by a forced air drying mode, drying at 80-100 ℃ for 10-20min to evaporate the solvent completely, oxidizing at 450-500 ℃ for 10-15min in a muffle furnace, taking out the titanium substrate after the titanium substrate is completely cooled, carrying out soaking, drying and high-temperature oxidation again, repeating the steps of cooling for 15-20 times, slowly heating to 450-500 ℃ in the muffle furnace for the last time, keeping the constant temperature for 1-1.5h, cooling to room temperature in the furnace, and taking out the titanium substrate with the RuO 2+SnO2 intermediate layer;
(4) Preparation of active layer: ultrasonically cleaning the titanium substrate obtained in the process (3), taking the cleaned titanium substrate as a cathode, taking a SnO 2 -based electrode as an anode, and electrodepositing the titanium substrate in a tin-antimony electrodepositing solution at a temperature of 25-30 ℃ for 50-70min at a constant current density of 15-20mA/cm 2; and after the electrodeposition is finished, carrying out high-temperature thermal oxidation in a heating furnace, heating to 450-500 ℃ at a heating rate of 5-10 ℃/min, keeping the temperature for 2-2.5h, then slowly cooling to room temperature in the furnace, and taking out to obtain the SnO 2+Sb2O3 active layer, thereby obtaining the titanium anode plate for water treatment.
2. The method for preparing a titanium anode plate for water treatment according to claim 1, wherein in the process (2): the electrolytic oxidation solution contains 1-2% of ammonium bifluoride and 20-25% of Tetrahydrofuran (THF).
3. The method for preparing a titanium anode plate for water treatment according to claim 1, wherein in the process (3): the alcohol solvent is a mixed solvent of isopropyl alcohol and n-butanol with the same volume, the volume ratio of hydrochloric acid to the alcohol solvent is 1:15-20, and the molar mass ratio of ruthenium ions to tin ions in the solution is n (Ru 3+)：n(Sn4+) =3-4:10.
4. The method for preparing a titanium anode plate for water treatment according to claim 1, wherein in the process (4): the tin-antimony electrodeposition liquid takes 10-14 parts of sodium stannate, 2-5 parts of antimony trichloride, 12-17 parts of citric acid, 3-5 parts of sodium pyrophosphate and 0.2-0.4 part of piperonal as main components, and the concentration of Sn 4+ in the tin-antimony electrodeposition liquid is 0.2-0.25mol/L.
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