CN109534460B - Titanium electrode and preparation method and application thereof - Google Patents
Titanium electrode and preparation method and application thereof Download PDFInfo
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- CN109534460B CN109534460B CN201811596201.7A CN201811596201A CN109534460B CN 109534460 B CN109534460 B CN 109534460B CN 201811596201 A CN201811596201 A CN 201811596201A CN 109534460 B CN109534460 B CN 109534460B
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- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 title claims abstract description 146
- 239000010936 titanium Substances 0.000 title claims abstract description 127
- 229910052719 titanium Inorganic materials 0.000 title claims abstract description 126
- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- 239000000758 substrate Substances 0.000 claims abstract description 64
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims abstract description 56
- 229910052709 silver Inorganic materials 0.000 claims abstract description 55
- 239000004332 silver Substances 0.000 claims abstract description 55
- 238000000034 method Methods 0.000 claims abstract description 43
- PEXQGCJZJMEHKN-UHFFFAOYSA-N [Ti].[Sn].[Bi] Chemical compound [Ti].[Sn].[Bi] PEXQGCJZJMEHKN-UHFFFAOYSA-N 0.000 claims abstract description 28
- 238000000137 annealing Methods 0.000 claims abstract description 12
- 238000004065 wastewater treatment Methods 0.000 claims abstract description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 21
- 238000000576 coating method Methods 0.000 claims description 16
- 239000002243 precursor Substances 0.000 claims description 16
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 15
- 238000005406 washing Methods 0.000 claims description 15
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 12
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 11
- 239000003513 alkali Substances 0.000 claims description 11
- 229910052797 bismuth Inorganic materials 0.000 claims description 11
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims description 11
- 239000002253 acid Substances 0.000 claims description 10
- 229910052718 tin Inorganic materials 0.000 claims description 10
- 238000001755 magnetron sputter deposition Methods 0.000 claims description 8
- 229910021626 Tin(II) chloride Inorganic materials 0.000 claims description 7
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 7
- 238000005488 sandblasting Methods 0.000 claims description 7
- AXZWODMDQAVCJE-UHFFFAOYSA-L tin(II) chloride (anhydrous) Chemical compound [Cl-].[Cl-].[Sn+2] AXZWODMDQAVCJE-UHFFFAOYSA-L 0.000 claims description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 6
- 238000004070 electrodeposition Methods 0.000 claims description 5
- 238000009713 electroplating Methods 0.000 claims description 5
- 238000001704 evaporation Methods 0.000 claims description 5
- 230000001680 brushing effect Effects 0.000 claims description 4
- 230000008020 evaporation Effects 0.000 claims description 4
- 238000000227 grinding Methods 0.000 claims description 4
- 235000006408 oxalic acid Nutrition 0.000 claims description 4
- 238000005229 chemical vapour deposition Methods 0.000 claims description 3
- 238000007598 dipping method Methods 0.000 claims description 3
- 238000004528 spin coating Methods 0.000 claims description 3
- JHXKRIRFYBPWGE-UHFFFAOYSA-K bismuth chloride Chemical compound Cl[Bi](Cl)Cl JHXKRIRFYBPWGE-UHFFFAOYSA-K 0.000 claims description 2
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 claims description 2
- 239000002904 solvent Substances 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 3
- 238000007740 vapor deposition Methods 0.000 claims 2
- 238000004506 ultrasonic cleaning Methods 0.000 claims 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 15
- 239000001301 oxygen Substances 0.000 abstract description 15
- 229910052760 oxygen Inorganic materials 0.000 abstract description 15
- 238000002161 passivation Methods 0.000 abstract description 6
- 230000008569 process Effects 0.000 abstract description 5
- 239000003344 environmental pollutant Substances 0.000 abstract description 4
- 231100000719 pollutant Toxicity 0.000 abstract description 4
- 239000002351 wastewater Substances 0.000 abstract description 4
- 239000010410 layer Substances 0.000 description 62
- 239000000243 solution Substances 0.000 description 33
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 19
- 239000008367 deionised water Substances 0.000 description 12
- 229910021641 deionized water Inorganic materials 0.000 description 12
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- 238000009210 therapy by ultrasound Methods 0.000 description 9
- 238000004140 cleaning Methods 0.000 description 8
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 8
- 229910001887 tin oxide Inorganic materials 0.000 description 7
- 229910000831 Steel Inorganic materials 0.000 description 6
- 238000001035 drying Methods 0.000 description 6
- 239000010959 steel Substances 0.000 description 6
- 239000011248 coating agent Substances 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 238000000151 deposition Methods 0.000 description 5
- 235000019441 ethanol Nutrition 0.000 description 5
- 239000011229 interlayer Substances 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 239000002932 luster Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 3
- 238000000861 blow drying Methods 0.000 description 3
- 239000003792 electrolyte Substances 0.000 description 3
- 239000011159 matrix material Substances 0.000 description 3
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical group [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 244000137852 Petrea volubilis Species 0.000 description 2
- 239000006004 Quartz sand Substances 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 230000009849 deactivation Effects 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- MINVSWONZWKMDC-UHFFFAOYSA-L mercuriooxysulfonyloxymercury Chemical compound [Hg+].[Hg+].[O-]S([O-])(=O)=O MINVSWONZWKMDC-UHFFFAOYSA-L 0.000 description 2
- 229910000371 mercury(I) sulfate Inorganic materials 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- 229910021607 Silver chloride Inorganic materials 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 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
- 229910052786 argon Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 238000004210 cathodic protection Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000003618 dip coating Methods 0.000 description 1
- 239000004519 grease Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 238000005554 pickling Methods 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- NNFCIKHAZHQZJG-UHFFFAOYSA-N potassium cyanide Chemical compound [K+].N#[C-] NNFCIKHAZHQZJG-UHFFFAOYSA-N 0.000 description 1
- 238000007781 pre-processing Methods 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
Images
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
-
- 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
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
Abstract
The invention provides a titanium electrode and a preparation method and application thereof, and belongs to the technical field of electrodes. The titanium electrode comprises a titanium substrate, a silver intermediate layer and a bismuth titanium tin active layer; the silver intermediate layer is arranged on the surface of the titanium substrate, and the bismuth titanium tin active layer is arranged on the surface of one side of the silver intermediate layer, which is far away from the titanium substrate. The titanium electrode has higher oxygen evolution potential and longer service life. The preparation method comprises the following steps: preparing a silver intermediate layer on the surface of the titanium substrate, arranging a bismuth titanium tin active layer on the surface of one side of the silver intermediate layer, which is far away from the titanium substrate, and then carrying out annealing treatment. The method has the advantages of simple process, good repeatability and easy operation, can effectively delay the passivation speed of the titanium substrate, prolongs the service life of the electrode, and simultaneously enables the electrode to have higher oxygen evolution potential. The titanium electrode can be used in various wastewater treatment environments, and can effectively degrade pollutants in wastewater.
Description
Technical Field
The invention belongs to the technical field of electrodes, and particularly relates to a titanium electrode and a preparation method and application thereof.
Background
The coated titanium electrode, also called dimensionally stable anode, is widely used in fields of chlor-alkali industry, wastewater treatment, electroplating, cathodic protection, etc.
At present, the tin oxide electrode commonly used in the coating titanium electrode has short service life, and the large-scale application of the tin oxide electrode is severely limited.
Therefore, there is a need to develop a new coated titanium electrode that can replace tin oxide electrodes.
Disclosure of Invention
One of the objects of the present invention consists in providing a titanium electrode having a high oxygen evolution potential and a long working life.
The second purpose of the invention is to provide a preparation method of the titanium electrode, which has simple process, good repeatability and easy operation, can effectively delay the passivation speed of a titanium substrate, prolong the service life of the electrode and simultaneously enable the electrode to have higher oxygen evolution potential.
A further object of the invention consists in providing the use of the titanium electrode described above, for example for wastewater treatment.
The technical problem to be solved by the invention is realized by adopting the following technical scheme:
the embodiment of the invention provides a titanium electrode, which comprises a titanium substrate, a silver intermediate layer and a bismuth titanium tin active layer; the silver intermediate layer is arranged on the surface of the titanium substrate, and the bismuth titanium tin active layer is arranged on the surface of one side of the silver intermediate layer, which is far away from the titanium substrate.
The invention also provides a preparation method of the titanium electrode, which comprises the following steps: preparing a silver intermediate layer on the surface of the titanium substrate, arranging a bismuth titanium tin active layer on the surface of one side of the silver intermediate layer, which is far away from the titanium substrate, and then carrying out annealing treatment.
The invention also provides an application of the titanium electrode, for example, the titanium electrode can be used for wastewater treatment.
The titanium electrode and the preparation method and application thereof in the embodiment of the invention have the beneficial effects that:
the titanium electrode provided by the preferred embodiment of the invention has a higher oxygen evolution potential and a longer service life. The preparation method has the advantages of simple process, good repeatability and easy operation, can effectively delay the passivation speed of the titanium substrate, prolongs the service life of the electrode, and simultaneously ensures that the electrode has higher oxygen evolution potential. The titanium electrode can be used for wastewater treatment and can effectively degrade pollutants in wastewater.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings needed to be used in the embodiments will be briefly described below, it should be understood that the following drawings only illustrate some embodiments of the present invention and therefore should not be considered as limiting the scope, and for those skilled in the art, other related drawings can be obtained according to the drawings without inventive efforts.
FIG. 1 is a plot of the voltammetric performance of a titanium electrode provided in example 1 of Experimental example 1 of the present application;
FIG. 2 is a graph of potential versus time for a titanium electrode provided in example 1 of test example 1 of the present application.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.
The technical solution of the present application will be described in detail below.
The titanium electrode comprises a titanium substrate, a silver intermediate layer and a bismuth titanium tin active layer; the silver intermediate layer is arranged on the surface of the titanium substrate, and the bismuth titanium tin active layer is arranged on the surface of one side of the silver intermediate layer, which is far away from the titanium substrate.
The inventor finds that the reason that the short service life of the tin oxide electrode commonly used at present can be caused by a titanium dioxide passivation film generated between the tin oxide material and the substrate in the catalytic oxidation process, and the passivation film hinders the electron transfer and finally leads to the deactivation of the electrode. In view of this, the inventors herein have incorporated an intermediate layer between the substrate and the bismuth titanium tin active layer that prevents contact between the oxygen atoms and the titanium substrate to improve the electrode operating life.
The intermediate layer is set as a silver intermediate layer, so that the intermediate layer has strong chemical stability, is resistant to acid and alkali corrosion and difficult to oxidize, and the price of silver is lower than that of platinum group metal. Furthermore, the bismuth, the titanium and the tin form an active layer together, the active layer has stronger binding force with the middle layer, so that the whole electrode structure is compact and firm, and the active layer is more stable compared with the traditional antimony doped tin oxide coating, so that the titanium electrode has higher oxygen evolution potential, and has stronger catalytic capability.
In the present application, the thickness of the silver intermediate layer may be 1 to 106nm, such as 1nm, 10nm, 50nm, 100nm, 500nm, 1000nm, 5000nm, 10nm4nm、5×104nm、105nm、5×105nm or 106nm and the likeAnd may be 1 to 106Any thickness value in the nm range.
Further, the thickness of the silver intermediate layer may be 10 a2-105nm, further, the thickness of the silver intermediate layer may be 103-104nm。
In some embodiments, the total thickness of the silver intermediate layer and the bismuth titanium tin active layer is no more than 10 μm, and may be, for example, 2 μm, 3 μm, 4 μm, 5 μm, 6 μm, 7 μm, 8 μm, 9 μm, 10 μm, or the like.
In the present application, the molar ratio of bismuth, titanium and tin in the bismuth titanium tin active layer may be 1 to 10: 20-50: 70-100, i.e. the molar ratio of bismuth, titanium and tin in the bismuth titanium tin active layer can be freely combined in the ranges of 1-10, 20-50 and 70-100 respectively, for example, the molar ratio of the three can be 1: 20: 70. 1: 50: 100. 10: 20: 70. 10: 50: 100 or 5: 35: 85, etc.
In the present application, the titanium substrate includes a titanium plate, a titanium mesh or a titanium rod, and the size thereof can be determined according to actual use conditions.
In addition, the application also provides a preparation method of the titanium electrode, which comprises the following steps: preparing a silver intermediate layer on the surface of the titanium substrate, arranging a bismuth titanium tin active layer on the surface of one side of the silver intermediate layer, which is far away from the titanium substrate, and then carrying out annealing treatment.
Wherein, the preparation of the silver intermediate layer comprises the following steps: the surface of the titanium substrate is covered with silver by a method such as magnetron sputtering, electroplating, evaporation plating or chemical vapor deposition to form a silver intermediate layer of a desired thickness.
In some embodiments, the method further comprises pre-treating the titanium substrate prior to disposing the intermediate layer of silver. The pre-processing may include, for example: and (3) carrying out grinding or sand blasting treatment, alkali washing and acid washing on the titanium matrix.
Alternatively, the grinding may be repeated rubbing the titanium substrate with 40-800 mesh sandpaper until the titanium substrate exhibits a metallic luster. The sand blasting treatment can be to use quartz sand to punch uniformly and densely distributed pits on the surface of the titanium substrate. Impurities and titanium oxide attached to the surface of the titanium substrate can be removed through polishing or sand blasting, the specific surface area of the titanium substrate can be increased through sand blasting, and the adhesive force of the coating is improved.
Alternatively, the alkali washing can be heating in NaOH solution with concentration of 20-40 wt% for 1-3h at 80-95 deg.C; or ultrasonically cleaning in acetone solution for 10-30min, and removing organic matters such as grease on the titanium substrate by alkali cleaning.
Preferably, the acid washing may be heating in oxalic acid of 10-40 wt% concentration or hydrochloric acid of 45-55 vol% (preferably 50 vol%) at 80-95 deg.C for 1-3 h. Uneven pitted surface is etched on the surface of the titanium matrix through acid washing, so that the binding force between the coating and the matrix is enhanced. The titanium substrate can be blow-dried with a nitrogen stream after pickling.
Further, the preparation of the bismuth titanium tin active layer may include: and covering the surface of one side of the silver intermediate layer far away from the titanium substrate with a precursor solution containing bismuth, titanium and tin to form a bismuth-titanium-tin active layer. The coating method may include, but is not limited to, a brushing method, a dropping coating method, a dip-coating method, a spin coating method, an electrodeposition method, a magnetron sputtering method, or an evaporation method.
In some embodiments, the precursor solution may be formed from BiCl3、SnCl2·2H2O and butyl titanate are mixed under the condition of taking absolute ethyl alcohol as a solvent. Specifically, for example, BiCl may be used3And SnCl2·2H2Dissolving O in absolute ethyl alcohol, then adding butyl titanate, and then using ethyl alcohol to fix the volume to obtain the precursor liquid.
Further, after the precursor liquid is applied, annealing treatment is performed to convert all non-oxides into oxides and form an electrode in which each layer is firmly bonded. Alternatively, the annealing treatment may be performed under conditions of 450-600 deg.C (e.g., 450 deg.C, 480 deg.C, 500 deg.C, 520 deg.C, 550 deg.C, 580 deg.C, 600 deg.C, etc.). Note that the annealing atmosphere may be performed in an atmospheric environment or an oxygen environment.
In the method, the surface of the titanium substrate is plated with the silver intermediate layer, and the bismuth titanium tin active layer is prepared on the surface of the silver intermediate layer, so that the prepared electrode can be more electrically conductive than the conventional electrodeThe service life is greatly improved (for example, the service life can be more common Ti/Sb-SnO2The electrode is improved by about 5 times), and simultaneously has high oxygen evolution potential (for example, when 0.5mol/L sulfuric acid is used as an electrolyte, and a mercurous sulfate electrode is used as a reference electrode, the oxygen evolution potential can reach 2.0V).
In addition, the application also provides an application of the titanium electrode, for example, the titanium electrode can be used for wastewater treatment, and pollutants in wastewater can be effectively degraded.
The features and properties of the present invention are described in further detail below with reference to examples.
Example 1
Pretreatment of a titanium substrate:
and repeatedly grinding the titanium substrate by using 80-mesh sand paper and 400-mesh sand paper in sequence until the titanium plate presents metallic luster. And (3) carrying out ultrasonic treatment on the ground titanium substrate for 10min by using deionized water, then placing the titanium substrate into a 40 wt% NaOH solution, and heating the titanium substrate for 1h under the condition of a water bath at 95 ℃. After alkali washing, the titanium sheet is taken out and is subjected to ultrasonic treatment for 10min by using deionized water, and then the titanium sheet is placed in 50 vol% HCl solution and is kept for 1 hour under the water bath condition of 90 ℃. And ultrasonically cleaning the steel plate by using deionized water after acid cleaning, and blow-drying the steel plate by using nitrogen flow.
Preparation of the intermediate layer:
and preparing a silver intermediate layer with the thickness of 100nm on the treated titanium substrate by a magnetron sputtering method. Background vacuum at deposition of 4.5X 10-4Pa, the flow of the introduced argon is 20sccm, and the working pressure is controlled to be 0.5 Pa. The temperature of the substrate during deposition was 25 ℃.
Preparation of the active layer:
1.5767g of BiCl were weighed out accurately3And 11.2825g of SnCl2·2H2Dissolving O in 30ml of absolute ethyl alcohol, adding 5.1054g of butyl titanate into the solution, transferring the solution into a 50ml volumetric flask, and adding ethanol to a constant volume to prepare a precursor solution.
Dipping a proper amount of precursor solution by a brush, repeatedly brushing the precursor solution on the titanium plate plated with the silver interlayer, placing the titanium plate in a drying box at 100 ℃ for drying for 5min after the coating solution uniformly covers the whole titanium plate, taking out the titanium plate, and then placing the titanium plate in a muffle furnace at 500 ℃ for annealing for 5 min. The above coating process was repeated 20 times and the last anneal was held for 1 hour. Taking out and naturally cooling to obtain the required electrode.
Example 2
Pretreatment of a titanium substrate:
the titanium substrate is subjected to sand blasting treatment by using 220-mesh quartz sand. And (3) carrying out ultrasonic treatment on the titanium substrate subjected to sand blasting for 10min by using deionized water, and then placing the titanium substrate in an acetone solution for 40min by ultrasonic treatment. After deoiling, taking out the titanium sheet, performing ultrasonic treatment for 10min by using deionized water, then placing the titanium sheet into 10 wt% oxalic acid solution, and keeping the titanium sheet for 1 hour under the condition of water bath at the temperature of 95 ℃. And after acid washing, ultrasonically washing the titanium plate in deionized water, and then blowing the titanium plate by using nitrogen flow for later use.
Preparation of the intermediate layer:
and preparing a silver intermediate layer with the thickness of 1000nm on the treated titanium substrate by an electrodeposition method. Silver foil with the purity of 99.99 percent is taken as an anode, a titanium substrate is taken as a cathode, the electrolyte is a mixed solution of silver chloride (30g/L), potassium cyanide (60g/L) and potassium carbonate (15g/L), and the current density is 10mA/cm2And depositing for 60 s.
Preparation of the active layer:
1.5767g of BiCl were weighed out accurately3And 11.2825g of SnCl2·2H2Dissolving O in 30ml of absolute ethyl alcohol, adding 5.1054g of butyl titanate into the solution, transferring the solution into a 50ml volumetric flask, and adding ethanol to a constant volume to prepare a precursor solution.
And (3) placing the treated titanium plate on a vacuum spin coater, dropwise adding a proper amount of prepared precursor liquid by using a suction pipe, setting the rotation speed of the spin coater to be 2500r/min, rotating for 30s, then placing the coated titanium plate in a drying box at 80 ℃ for drying for 10min, taking out the titanium plate, and then placing the titanium plate in a muffle furnace at 550 ℃ for annealing for 5 min. The above coating process was repeated 20 times and the last anneal was held for 1 h. Taking out and naturally cooling to obtain the required electrode.
Example 3
Pretreatment of a titanium substrate:
the titanium mesh was repeatedly polished with 40-mesh and 800-mesh sandpaper until the titanium mesh exhibited a metallic luster. And (3) carrying out ultrasonic treatment on the ground titanium mesh for 20min by using deionized water, then placing the titanium mesh in a 20 wt% NaOH solution, and heating the titanium mesh for 3h under the condition of a water bath at 80 ℃. After alkali washing, the titanium mesh is taken out and is subjected to ultrasonic treatment for 10min by using deionized water, and then the titanium mesh is placed in a 10 wt% HCl solution and is kept for 3 hours under the condition of 80 ℃ water bath. And ultrasonically cleaning the steel plate by using deionized water after acid cleaning, and blow-drying the steel plate by using nitrogen flow.
Preparation of the intermediate layer:
preparing the titanium substrate with the thickness of 10 by an electroplating method5A nm silver interlayer.
Preparation of the active layer:
weighing BiCl3And SnCl2·2H2Dissolving O in absolute ethyl alcohol, adding butyl titanate into the solution, transferring the solution into a 50ml volumetric flask, adding ethanol to a constant volume, and preparing the bismuth, titanium and tin with a molar ratio of 1: 20: 70 precursor liquid.
And depositing the precursor solution on the surface of the side, away from the titanium mesh, of the silver interlayer by adopting an electrodeposition method, then drying for 10min, and then placing in a muffle furnace at 450 ℃ for annealing for 8 min. The above coating process was repeated 25 times and the last anneal was held for 1 h. Taking out and naturally cooling to obtain the required electrode. Wherein the total thickness of the silver intermediate layer and the bismuth titanium tin active layer is 2 μm.
Example 4
Pretreatment of a titanium substrate:
the titanium rod was repeatedly polished with 200-mesh and 400-mesh sandpaper until the titanium rod exhibited a metallic luster. And (3) carrying out ultrasonic treatment on the polished titanium rod for 20min by using deionized water, then placing the titanium rod into a 30 wt% NaOH solution, and heating the titanium rod for 2h under the water bath condition of 90 ℃. After alkali washing, the titanium rod is taken out and is subjected to ultrasonic treatment for 10min by using deionized water, and then the titanium rod is placed in 25 wt% oxalic acid solution and is kept for 2 hours under the condition of water bath at the temperature of 95 ℃. And ultrasonically cleaning the steel plate by using deionized water after acid cleaning, and blow-drying the steel plate by using nitrogen flow.
Preparation of the intermediate layer:
preparing the titanium substrate with the thickness of 10 by an evaporation coating method4A nm silver interlayer.
Preparation of the active layer:
weighing BiCl3And SnCl2·2H2Dissolving O in absolute ethyl alcohol, adding butyl titanate into the solution, transferring the solution into a 50ml volumetric flask, adding ethanol to a constant volume to obtain bismuth and titaniumAnd the molar ratio of tin is 10: 50: 100 precursor solution.
Depositing the precursor solution on the surface of the side, away from the titanium rod, of the silver interlayer by adopting a magnetron sputtering method, then drying for 10min, and then placing in a muffle furnace at 600 ℃ for annealing for 10 min. The above coating process was repeated 25 times and the last anneal was held for 1 h. Taking out and naturally cooling to obtain the required electrode. Wherein the total thickness of the silver intermediate layer and the bismuth titanium tin active layer is 5.5 mu m.
Example 5
This example differs from example 1 in that: the molar ratio of bismuth, titanium and tin in the bismuth titanium tin active layer is 5: 35: 85.
test examples
Taking the electrode obtained in the example 1 as an example, the performance test is carried out on the electrode, and the test selects a standard three-electrode system electrolytic cell, the electrode to be tested is a working electrode, the counter electrode selects a platinum electrode, mercurous sulfate is a reference electrode, and the electrolyte is 0.5mol/L sulfuric acid solution. In the enhanced life test, the current density is 100mA/cm2The electrode deactivation was measured as a 5V increase in cell pressure. The results are shown in FIGS. 1 and 2. As can be seen from FIG. 1, the oxygen evolution potential of this electrode is 2.0V. As can be seen from fig. 2, the enhanced service life of the electrode is about 27 hours.
Comparative examples 1 to 2 were set, and comparative example 1 was different from example 1 in that there was no silver intermediate layer, and comparative example 2 was different from example 1 in that the material of the active layer was antimony-doped tin oxide, and the results of the comparative example 1, and comparative example 2 were shown in table 1.
TABLE 1 electrode Performance
| Example 1 | |
|
|
| Oxygen evolution potential | 2.0V | 1.9V | 2.0V |
| Service life | 27h | 3h | 5h |
As can be seen from table 1, in the present application, by further disposing the silver intermediate layer between the titanium substrate and the active layer or combining the active components of the intermediate layer with bismuth, titanium and tin, the oxygen evolution potential and the service life of the obtained titanium electrode can be significantly improved.
In conclusion, the titanium electrode provided by the application has higher oxygen evolution potential and longer service life. The preparation method has the advantages of simple process, good repeatability and easy operation, can effectively delay the passivation speed of the titanium substrate, prolongs the service life of the electrode, and simultaneously ensures that the electrode has higher oxygen evolution potential. The titanium electrode can be used for wastewater treatment and can effectively degrade pollutants in wastewater.
The above is only a preferred embodiment of the present invention, and is not intended to limit the present invention, and various modifications and changes will occur to those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (11)
1. The titanium electrode is characterized by comprising a titanium substrate, a silver intermediate layer and a bismuth titanium tin active layer; the silver intermediate layer is arranged on the surface of the titanium substrate, and the bismuth titanium tin active layer is arranged on the surface of one side of the silver intermediate layer, which is far away from the titanium substrate;
the thickness of the silver intermediate layer is 1-106nm; the total thickness of the silver intermediate layer and the bismuth titanium tin active layer is not more than 10 mu m;
the molar ratio of bismuth to titanium to tin in the bismuth-titanium-tin active layer is 1-10: 20-50: 70-100 parts of;
the preparation of the silver intermediate layer comprises the following steps: covering silver on the surface of the titanium substrate by adopting a magnetron sputtering method, an electroplating method, an evaporation coating method or a chemical vapor deposition method to form the silver intermediate layer;
the preparation of the bismuth titanium tin active layer comprises the following steps: covering a precursor solution containing bismuth, titanium and tin on the surface of one side of the silver intermediate layer, which is far away from the titanium substrate, so as to form the bismuth-titanium-tin active layer; the covering method includes a brushing method, a dropping coating method, a dipping and pulling method, a spin coating method, an electrodeposition method, a magnetron sputtering method or a vapor deposition method.
2. The titanium electrode of claim 1, wherein said titanium substrate comprises a titanium plate, a titanium mesh, or a titanium rod.
3. The method for producing a titanium electrode according to claim 1 or 2, comprising the steps of: preparing the silver intermediate layer on the surface of the titanium substrate, arranging the bismuth titanium tin active layer on the surface of one side of the silver intermediate layer, which is far away from the titanium substrate, and then carrying out annealing treatment.
4. The production method according to claim 3, wherein the production of the silver intermediate layer comprises: and covering the surface of the titanium substrate with silver by adopting a magnetron sputtering method, an electroplating method, an evaporation coating method or a chemical vapor deposition method to form the silver intermediate layer.
5. The method according to claim 3, wherein the preparing the bismuth titanium tin active layer comprises: covering a precursor solution containing bismuth, titanium and tin on the surface of one side of the silver intermediate layer, which is far away from the titanium substrate, so as to form the bismuth-titanium-tin active layer; the covering method includes a brushing method, a dropping coating method, a dipping and pulling method, a spin coating method, an electrodeposition method, a magnetron sputtering method or a vapor deposition method.
6. The method of claim 5, wherein the precursor solution is BiCl3、SnCl2·2H2O and butyl titanate are mixed under the condition of taking absolute ethyl alcohol as a solvent.
7. The method as claimed in claim 3, wherein the annealing treatment is performed at a temperature of 450-600 ℃.
8. The method of claim 3, further comprising, prior to disposing the silver intermediate layer, pre-treating the titanium substrate;
the pretreatment comprises the following steps: and (3) carrying out grinding or sand blasting treatment, alkali washing and acid washing on the titanium substrate.
9. The preparation method according to claim 8, characterized in that the alkali washing is carried out by heating in NaOH solution with concentration of 20-40 wt% for 1-3h at 80-95 ℃; or, the alkali washing is ultrasonic cleaning in acetone solution for 10-30 min.
10. The method according to claim 9, wherein the acid washing is performed by heating in oxalic acid of 10 to 40 wt% or hydrochloric acid of 45 to 55 vol% at 80 to 95 ℃ for 1 to 3 hours.
11. Use of a titanium electrode according to claim 1 or 2 for wastewater treatment.
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