CN106745557A - A kind of titanium-based tin iridium oxide electrode and preparation method thereof - Google Patents
A kind of titanium-based tin iridium oxide electrode and preparation method thereof Download PDFInfo
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- CN106745557A CN106745557A CN201710145620.8A CN201710145620A CN106745557A CN 106745557 A CN106745557 A CN 106745557A CN 201710145620 A CN201710145620 A CN 201710145620A CN 106745557 A CN106745557 A CN 106745557A
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Abstract
The present invention relates to a kind of titanium-based tin iridium oxide electrode and preparation method thereof, belong to electrode field.The preparation method of above-mentioned titanium-based tin iridium oxide electrode includes：Titanium plate is polished successively, oil removing, immersion etching, obtain with pitted skin titanium plate layer.By weight 35:24 by SnCl4·5H2O and H2IrCl6·6H2O is dissolved in presoma solvent, obtains presoma masking liquid；Presoma masking liquid is painted on the surface of titanium plate layer, first coating is obtained, dried and first sintering.Manganese nitrate solution is painted on surface of the first coating away from titanium plate layer, second coating is obtained；Dry and second sintering second coating, obtain titanium-based tin iridium oxide electrode.The preparation method is simple, easy to operate.The titanium-based tin iridium oxide electrode being prepared by above-mentioned preparation method has electro-catalysis ability higher, has preferable effect to the treatment of salt-containing organic wastewater.
Description
Technical field
The present invention relates to electrode field, and in particular to a kind of titanium-based tin iridium oxide electrode and preparation method thereof.
Background technology
With expanding economy, the quantity of biodegradable organic compoundses is growing day by day with species in industrial wastewater, and these have
The harmful high concentration bio-refractory organic wastewater of poison governs the industries such as the chemical industry, pharmacy, printing and dyeing, papermaking of China all the time
Sustainable development, also contribute to its people normal life and physical and mental health.A large amount of industrial wastewaters that these industries are discharged, tool
The features such as having various complicated component, species, bio-refractory, COD high, poisonous and harmful, some or even teratogenesis,
Carcinogenic, mutagenic " three cause " pollutant, if do not controlled effectively and processed, will cause extremely serious dirt to environment
Dye and destruction, the normal life of economic development and its people to China cause immeasurable loss.
Carry out the comprehensive regulation of this kind of industrial wastewater, it has also become contemporary environmental scientific research worker problem demanding prompt solution it
One.Early 1960s, with developing rapidly for mass transfer theory, material science and power industry, electrochemical advanced oxidation
Technology gradually attract attention.Electrochemical techniques with its distinctive electro-catalysis function, good treatment effect and preferably
Compatibility, show good application prospect in water treatment field.
Anode is in vital status in electrochemical oxidation technology, and efficient electrochemical oxidation technology is successfully transported
Water treatment field is used, especially in salt-containing organic wastewater treatment, must just improve the premium properties of anode material.Existing gold
Easily there is dissolution phenomenon in category electrode, cause anode loss in electrochemical oxidation process, and then introduce new miscellaneous in the solution
Matter.Even if less soluble inert electrode (platinum electrode), the problem for being easy to pollute and cause electrode inactivation is there is also.Secondly, carbon
Traditionally the corrosion resistance of plain electrode is better than metal electrode, but its electro-catalysis efficiency lags far behind metal electrode.Metal
Oxide electrode is the most promising electro catalytic electrode at present in terms of environmental contaminants removal.Compared to metal electrode,
Oxide electrode is less susceptible to be contaminated；Compared to carbon pole, oxide electrode has more excellent electro catalytic activity.
The content of the invention
It is an object of the invention to provide a kind of titanium-based tin iridium oxide electrode, the titanium-based tin iridium oxide electrode have compared with
Electro-catalysis ability high, has preferable effect to the treatment of salt-containing organic wastewater.
Another object of the present invention is to provide a kind of preparation method of above-mentioned titanium-based tin iridium oxide electrode, the preparation side
Method is simple, easy to operate.
The present invention is solved its technical problem and is realized using following technical scheme：
The present invention proposes a kind of titanium-based tin iridium oxide electrode, and it includes titanium plate layer, first coating and second coating；First
Coating is the tin iridium oxide coating for being plated on titanium plate layer surface, second coating be plated on first coating away from titanium plate layer side table
The MnO in face2Coating.
The present invention also proposes the preparation method of above-mentioned titanium-based tin iridium oxide electrode, comprises the following steps：To titanium plate successively
Polished, oil removing, immersion etching, obtain with pitted skin titanium plate layer.
By weight 3-5:2-4 is by SnCl4·5H2O and H2IrCl6·6H2O is dissolved in presoma solvent, obtains forerunner
Body masking liquid；Presoma masking liquid is painted on the surface of titanium plate layer, first coating is obtained, the first coating is applied for tin iridium oxide
Layer, wherein, presoma solvent be containing volume ratio be 1:The acid solution of 5-10 and the mixed solution of alcoholic solution.
Dry and first sintering first coating, manganese nitrate solution is painted on table of the first coating away from titanium plate layer side
Face, obtains second coating, and the second coating is MnO2Coating.
Dry and second sintering second coating, obtain titanium-based tin iridium oxide electrode.
The beneficial effect of the preparation method of titanium-based tin iridium oxide electrode is in present pre-ferred embodiments：By SnCl4·
5H2O and H2IrCl6·6H2O is mixed with first coating, can be by the Sn contained by it4+Ion and Ir4+Ion improves leading for electrode
Electrically and electrocatalysis characteristic, hence it is evident that better than comprising only a kind of electrode of above-mentioned ion.And in first coating in the embodiment of the present invention
Surface away from titanium plate layer is coated with second coating, also as MnO2Coating, not only can further improve the electrocatalysis characteristic of electrode
With high-salt wastewater disposal ability, can also effectively improve while containing Sn4+Ion and Ir4+The stability of the electrode of ion.By the system
The titanium-based tin iridium oxide electrode that Preparation Method is prepared has electro-catalysis ability higher, to the treatment tool of salt-containing organic wastewater
There is preferable effect.
Brief description of the drawings
Technical scheme in order to illustrate more clearly the embodiments of the present invention, below will be attached to what is used needed for embodiment
Figure is briefly described, it will be appreciated that the following drawings illustrate only certain embodiments of the present invention, thus be not construed as it is right
The restriction of scope, for those of ordinary skill in the art, on the premise of not paying creative work, can also be according to this
A little accompanying drawings obtain other related accompanying drawings.
Fig. 1 is the structural representation of the titanium-based tin iridium oxide electrode that the embodiment of the present invention 1 is provided；
Fig. 2 is the structural representation of the titanium-based tin iridium oxide electrode that the embodiment of the present invention 2 is provided；
Fig. 3 is the structural representation of the titanium-based tin iridium oxide electrode that the embodiment of the present invention 3 to embodiment 5 is provided；
Fig. 4 is the structure under the second visual angle of the titanium-based tin iridium oxide electrode that the embodiment of the present invention 4 and embodiment 5 are provided
Schematic diagram.
Icon：100- titanium-based tin iridium oxide electrodes；110- titanium plates layer；120- coatings；121- first coatings；123- second
Coating；124- intermediate layers；The coatings of 125- the 3rd.
Specific embodiment
To make the purpose, technical scheme and advantage of the embodiment of the present invention clearer, below in conjunction with the embodiment of the present invention
In accompanying drawing, the technical scheme in the embodiment of the present invention is clearly and completely described.Obviously, described embodiment is
A part of embodiment of the present invention, rather than whole embodiments.Present invention implementation generally described and illustrated in accompanying drawing herein
The component of example can be arranged and designed with a variety of configurations.
Therefore, the detailed description of embodiments of the invention below to providing in the accompanying drawings is not intended to limit claimed
The scope of the present invention, but be merely representative of selected embodiment of the invention.Based on the embodiment in the present invention, this area is common
The every other embodiment that technical staff is obtained under the premise of creative work is not made, belongs to the model of present invention protection
Enclose.
In the description of the invention, it is necessary to illustrate, term " first ", " second ", " the 3rd " are only used for distinguishing description,
And it is not intended that indicating or implying relative importance.For the ordinary skill in the art, can be managed with concrete condition
Solve above-mentioned term concrete meaning in the present invention.
Present invention is specifically described below.
Titanium-based tin iridium oxide electrode of the invention includes titanium plate layer and coating.Coating is plated on the surface of titanium plate layer.Wherein,
Coating is divided into first coating and second coating again.First coating is plated on the surface of titanium plate layer, and it is remote that second coating is plated on first coating
From the surface of titanium plate layer.
Prepare and can obtain by the following method in the titanium-based tin iridium oxide electrode process titanium plate layer：Titanium plate is taken as ground,
And titanium plate is polished successively, oil removing and immersion etching.The cost performance of each titanium plate is contrasted, TA1 is preferably used in the present embodiment
Or any one in TA2 types is used as ground, and it is polished tentatively to remove the natural oxidizing layer on titanium plate surface, reduced
The cut of titanium-based plate surface, makes titanium-based plate surface show silvery white metallic luster.Specifically, for example can be using sand paper to titanium plate
Polished on surface.
The impurity such as greasy dirt are remained in order to avoid titanium plate surface, after polishing, titanium plate can be removed with akaline liquid
Oil operation.Specifically, the titanium plate after polishing can be for example immersed in saturation sodium hydroxide solution, boils 40-50min.Its
Principle is：NaOH can occur saponification with grease, generate the sodium salt and alcohol of corresponding organic acid.Because temperature is to hydrogen-oxygen
The dissolubility for changing sodium has considerable influence, and temperature is higher, and the solubility of NaOH is also bigger, therefore in order to improve speed oil and journey
Degree, the present embodiment step of deoiling is carried out under boiling conditions.
Because of the oxidizable generation titanium dioxide film in titanium plate surface, to remove the oxide layer on its surface, for example can be to oil removing after
Titanium plate carries out immersion etching processing.For example the titanium plate after oil removing is placed in 4-6h is soaked in soak.Alternatively, above-mentioned soak
At least two acidic materials in nitric acid, hydrochloric acid, sulfuric acid and oxalic acid can for example be contained.It is fiber crops that immersion is etched to titanium plate surface
Face, has no metallic luster, that is, obtain the titanium plate layer with pitted skin.The effect of the electrode reaction after coating is plated in view of the titanium plate layer later stage
Really, preferably by the thickness control of titanium plate layer in 1-2mm.
It is preferred that the immersion etching example in the present embodiment may include immersion etching for the first time, titanium plate that will be after oil removing is put
1-2h is soaked in 40-60 DEG C of the first soak.First soak can be for example 1 containing volume ratio:The nitric acid of 1-1.5 and
Hydrochloric acid.After through immersion of above-mentioned first time etching, titanium plate most surfaces are respectively formed pitted skin.
Further to improve the formation area of pitted skin, also second immersion etching can be carried out after first time immersion etching.
Preferably, the titanium plate after first time immersion etching is placed in 80-90 DEG C of the second soak and soaks 3-4h.Second soak
Can be for example 1 containing volume ratio:The sulfuric acid and oxalic acid of 1-3.Titanium plate after being soaked using different soaks, its pitted skin for being formed
It is evenly distributed in cellular, and space, is conducive to the combination of subsequent preparation process floating coat and titanium plate layer.
Then, coating treatment is carried out to titanium plate layer surface.The first coating for example on the plated surface of titanium plate layer, first painting
The thickness of layer is preferably controlled to 20-25 μm specifically, by weight 3-5:2-4 is by SnCl4·5H2O and H2IrCl6·6H2O dissolves
In presoma solvent, presoma masking liquid is obtained.It is preferred that presoma solvent be containing volume ratio be 1:The acid solution of 5-10
With the mixed solution of alcoholic solution.Wherein, acid solution can be selected from any one in concentrated hydrochloric acid, citric acid and acetic acid, and alcohol is molten
Liquid can be selected from any one in ethanol, isopropanol and ethylene glycol.In practical operation, can be by the SnCl of 3-5g4·5H2O and
The H of 2-4g2IrCl6·6H2O mixing is added in the mixed solution containing 1mL citric acid solutions and 5-10mL ethylene glycol solutions.Should
The viscosity of mixed solution is higher, can improve the adhesion of first coating and titanium plate layer, extends the service life of electrode.
Above-mentioned presoma masking liquid is uniformly painted on the surface of titanium plate layer, first coating is obtained, namely tin iridium oxide is applied
Layer.Then simultaneously first sintering first coating is dried, is tied to make first coating be tightly combined with titanium plate layer, and to improve the two
Intensity after conjunction.It is preferred that first sintering can sinter at least 25min under conditions of 350-450 DEG C.To strengthen first coating
Painting brushing effects, in practical operation, repeat brushing first coating and drying and first sintering.Hold, the present invention will
SnCl4·5H2O and H2IrCl6·6H2O is mixed with first coating, can be by Sn4+Ion and Ir4+Ion improves leading for electrode
Electrically and electrocatalysis characteristic, hence it is evident that better than comprising only a kind of electrode of above-mentioned ion.
But contain Sn simultaneously due to above-mentioned4+Ion and Ir4+The electrode stability of ion is not high, therefore the present invention is preferably
Second coating on the once sintered plated surface after first coating away from titanium plate layer, the second coating is preferably MnO2Coating, no
The electrocatalysis characteristic of electrode is only can further improve, can also be effectively improved while containing Sn4+Ion and Ir4+The electrode of ion
Stability.Specifically, for example manganese nitrate can be configured to manganese nitrate solution, the manganese nitrate solution is then painted on the first painting
Layer obtains second coating away from the surface of titanium plate layer, and the thickness of the second coating is preferably controlled to 40-60 μm.
Then dry and second sintering second coating, to make first coating be tightly combined with first coating, and improve
The two intensity after combining.It is preferred that second sintering can sinter 20-30min under conditions of 450-500 DEG C.To strengthen the
The painting brushing effects of two coatings, in practical operation, repeat brushing second coating and drying and second sinter.It is above-mentioned simultaneously
Contain tin iridium oxide coating and MnO2The titanium-based tin iridium oxide electrode of coating has stronger oxidability, the stabilization of electrode
Property and electric conductivity it is also relatively strong, can be used to process the organic wastewater containing heavy metal ion and saliferous.
Further to improve the oxygen evolution potential and corrosion resistance of titanium-based tin iridium oxide electrode in the present embodiment, improve organic
Water treatment effect, it is preferable that can also on plated surface of the second coating away from first coating the 3rd coating.3rd coating is for example
Can be the PbO containing rare-earth oxide2Coating.Wherein, rare-earth oxide preferably is selected from the oxygen of the oxide of yttrium, lanthanum
At least one in the oxide of compound and neodymium.
Specifically, by La2O3、Y2O3And Nd2O3In at least one rare-earth oxide and PbO2It is added to the water electric
Plating solution, the pH of above-mentioned electroplate liquid is adjusted to 2-2.5 with nitric acid, obtains acidic Bath.Then should under conditions of 70-80 DEG C
Acidic Bath is plated on surface of the second coating away from first coating, obtains the 3rd coating.The thickness of the 3rd coating for example may be used
Think 50-60 μm.
By plating the 3rd coating containing rare-earth oxide and brown lead oxide, titanium-based tin iridium oxide electrode surface
More fine and close, structure is more uniform complete.Also, in electrochemical reaction process, can be by the hydroxyl that produces oxidisability extremely strong
Free radical and nascent oxygen, difficult biochemical organic pollution of effectively degrading, it is to avoid other high-level oxidation technologies such as ozone oxidation,
Fenton reagent method need to add oxidant etc. and bring problem.Secondly, the rare-earth oxide in the 3rd coating can improve electrode
Oxygen evolution potential, reduce oxidation peak current so that effectively suppress electrochemical oxidation process in analysis oxygen side reaction, improve electric energy profit
With rate.Again, the titanium-based tin iridium oxide electrode containing the 3rd coating can degrade salt-containing organic wastewater at normal temperatures and pressures, degraded
Mild condition, process is simple, to equipment without strict demand.
Optionally, the present embodiment can also plate the intermediate layer containing Cu elements between second coating and the 3rd coating,
Further to improve the catalysis activity of electrode.Namely intermediate layer is plated on surface of the second coating near the 3rd coating side, the 3rd
Coating is plated on surface of the intermediate layer away from second coating side.The thickness in intermediate layer for example can be controlled in 5-10 μm.
By the coating containing multiple dope layers on the plated surface of titanium plate layer, make titanium-based tin iridium oxide in the present embodiment
The crystal of electrode surface is uniformly complete, contributes to the avtive spot of electrode surface to expose, and promotes the electrode to have with target contaminant
Effect contact, improves the mass transfer in course of reaction, while the stability and electric conductivity of electrode is strengthened, also improves the electricity of electrode
Catalysis activity, is conducive to migration, absorption and the desorption of pollutant, therefore, raising is reached to organic pollution, such as brine waste
The effect of degraded.
More preferably, above-mentioned titanium-based tin iridium oxide electrode for example can be in any in cross, flechette-type, flower-shape and square cards for learning characters shape
A kind of shape.But because the influence of electrode pair CURRENT DISTRIBUTION of different shapes is different, as more preferably, by titanium-based tin in the present embodiment
Iridium oxide electrode is set to ten thousand font electrodes, so that current expansion is the most uniform, electro-catalysis best results.
Feature of the invention and performance are described in further detail with reference to embodiments.
Embodiment 1
Titanium plate is cut into thickness and is the cross of 1mm, and its surface is polished with sand paper, then by after polishing
Titanium plate boils 40min with oil removing in being immersed in saturation sodium hydroxide solution.Then, the titanium plate after oil removing is placed in the first of 40 DEG C
Immersion for the first time etches 1h in soak, and it is 1 that first soak contains volume ratio:1 nitric acid and hydrochloric acid.Then again by first
Titanium plate after secondary immersion etching is placed in soaks 3h in 80 DEG C of the second soak, it is 1 that the second soak contains volume ratio:1 sulphur
Acid and oxalic acid.
By 3gSnCl4·5H2O and 2gH2IrCl6·6H2O is dissolved in mixed containing 1mL citric acids and 5mL ethylene glycol solutions
Close in solution, obtain presoma masking liquid.The presoma masking liquid is painted on 110 surface of titanium plate layer, 20 μm of first coating is obtained
121, dry and the first sintering 25min under conditions of 350 DEG C.
Then manganese nitrate solution is painted on surface of the first coating 121 away from titanium plate layer 110, obtains 40 μm of the second painting
Layer 123, dries and second sintering 20min under conditions of 450 DEG C, obtains titanium-based tin iridium oxide electrode as shown in Figure 1
100。
The titanium-based tin iridium oxide electrode 100 includes titanium plate layer 110 and coating 120.Coating 120 in the present embodiment includes
First coating 121 and second coating 123.Wherein, first coating 121 is plated on 110 surface of titanium plate layer, and second coating 123 is plated on the
Surface of one coating 121 away from 110 side of titanium plate layer.
Embodiment 2
Titanium plate is cut into thickness and is the flechette-type of 2mm, and its surface is polished with sand paper, then by the titanium after polishing
Plate boils 50min with oil removing in being immersed in saturation sodium hydroxide solution.Then, the titanium plate after oil removing is placed in 60 DEG C of the first leaching
Immersion for the first time etches 2h in bubble liquid, and it is 1 that first soak contains volume ratio:1.5 nitric acid and hydrochloric acid.Then again by first
Titanium plate after secondary immersion etching is placed in soaks 4h in 90 DEG C of the second soak, it is 1 that the second soak contains volume ratio:3 sulphur
Acid and oxalic acid.
By 5gSnCl4·5H2O and 4gH2IrCl6·6H2O is dissolved in mixed containing 1mL concentrated hydrochloric acids and 10mL aqueous isopropanols
Close in solution, obtain presoma masking liquid.The presoma masking liquid is painted on 110 surface of titanium plate layer, 25 μm of first coating is obtained
121, dry and the first sintering 30min under conditions of 450 DEG C.
Then manganese nitrate solution is painted on surface of the first coating 121 away from titanium plate layer 110, obtains 60 μm of the second painting
Layer 123, dries and second sintering 30min under conditions of 500 DEG C.
By La2O3And PbO2It is added to the water, and is 2 with nitre acid for adjusting pH, obtains acidic Bath.Then in 70 DEG C of bar
Above-mentioned acidic Bath is plated on surface of the second coating 123 away from first coating 121 under part, obtain that thickness is 50 μm the 3rd
Coating 125.Cooling, obtains titanium-based tin iridium oxide electrode 100 as shown in Figure 2.
The titanium-based tin iridium oxide electrode 100 includes titanium plate layer 110 and coating 120.Coating 120 in the present embodiment includes
First coating 121, the coating 125 of second coating 123 and the 3rd.Wherein, first coating 121 is plated on 110 surface of titanium plate layer, and second applies
Layer 123 is plated on surface of the first coating 121 away from 110 side of titanium plate layer, and the 3rd coating 125 is plated on second coating 123 away from the
The surface of the side of one coating 121.
Embodiment 3
Titanium plate is cut into thickness and is the flower-shape of 1.5mm, and its surface is polished with sand paper, then by after polishing
Titanium plate boils 45min with oil removing in being immersed in saturation sodium hydroxide solution.Then, the titanium plate after oil removing is placed in the first of 50 DEG C
Immersion for the first time etches 1.5h in soak, and it is 1 that first soak contains volume ratio:1.3 nitric acid and hydrochloric acid.Then again will
The titanium plate after immersion etching is placed in and 3.5h is soaked in 85 DEG C of the second soak for the first time, and it is 1 that the second soak contains volume ratio:
2 sulfuric acid and oxalic acid.
By 4gSnCl4·5H2O and 3gH2IrCl6·6H2It is molten that O is dissolved in the mixing containing 1mL acetic acid and 8mL ethanol solutions
In liquid, presoma masking liquid is obtained.The presoma masking liquid is painted on 110 surface of titanium plate layer, is dried and the under conditions of 400 DEG C
Once sintered 40min, repeats to brush, drying and first sintering 10 times, obtains 23 μm of first coating 121.
Then manganese nitrate solution is painted on surface of the first coating 121 away from titanium plate layer 110, is dried and in 480 DEG C
Under the conditions of second sintering 25min, repeat brushing second coating 123, dry and second sintering 10 times, obtain the second of 50 μm
Coating 123.
By Y2O3、Nd2O3And PbO2It is added to the water, and is 2.5 with nitre acid for adjusting pH, obtains acidic Bath.Then in 80
Above-mentioned acidic Bath is plated on surface of the second coating 123 away from first coating 121 under conditions of DEG C, thickness is obtained for 60 μm
The 3rd coating 125.
5 μm of intermediate layers 124 containing Cu are plated again towards the surface of the side of second coating 123 in first coating 121, are cooled down,
Obtain titanium-based tin iridium oxide electrode 100 as shown in Figure 2.
5 μm of intermediate layers 124 containing Cu are plated again towards the surface of the side of the 3rd coating 125 in second coating 123, are cooled down,
Obtain titanium-based tin iridium oxide electrode 100 as shown in Figure 3.
The titanium-based tin iridium oxide electrode 100 includes titanium plate layer 110 and coating 120.Coating 120 in the present embodiment includes
First coating 121, second coating 123, the coating 125 of intermediate layer 124 and the 3rd.Wherein, first coating 121 is plated on titanium plate layer 110
Surface, second coating 123 is plated on surface of the first coating 121 away from 110 side of titanium plate layer, and intermediate layer 124 is plated on second coating
123 away from first coating 121 surface, the 3rd coating 125 is plated on surface of the intermediate layer 124 away from the side of second coating 123.
Embodiment 4
Titanium plate is cut into thickness and is the square cards for learning characters shape of 1.5mm, and its surface is polished with sand paper, after then polishing
Titanium plate be immersed in saturation sodium hydroxide solution in boil 45min with oil removing.Then, the titanium plate after oil removing is placed in the of 50 DEG C
Immersion for the first time etches 1.5h in one soak, and it is 1 that first soak contains volume ratio:1.3 nitric acid and hydrochloric acid.Then again
Titanium plate after first time immersion etching is placed in 3.5h is soaked in 85 DEG C of the second soak, the second soak contains volume ratio and is
1:2 sulfuric acid and oxalic acid.
By 4gSnCl4·5H2O and 3gH2IrCl6·6H2It is molten that O is dissolved in the mixing containing 1mL acetic acid and 8mL ethanol solutions
In liquid, presoma masking liquid is obtained.The presoma masking liquid is painted on 110 surface of titanium plate layer, is dried and the under conditions of 400 DEG C
Once sintered 45min, repeats to brush, drying and first sintering 20 times, obtains 25 μm of first coating 121.
Then manganese nitrate solution is painted on surface of the first coating 121 away from titanium plate layer 110, is dried and in 480 DEG C
Under the conditions of second sintering 25min, repeat brushing second coating 123, dry and second sintering 20 times, obtain the second of 50 μm
Coating 123.
By La2O3、Nd2O3And PbO2It is added to the water, and is 2.3 with nitre acid for adjusting pH, obtains acidic Bath.Then in 75
Above-mentioned acidic Bath is plated on surface of the second coating 123 away from first coating 121 under conditions of DEG C, plating 10 times is repeated,
Obtain the 3rd coating 125 that thickness is 55 μm.
10 μm of intermediate layers 124 containing Cu are plated again towards the surface of the side of second coating 123 in first coating 121, are cooled down,
Obtain titanium-based tin iridium oxide electrode 100 as shown in Figure 3.
10 μm of intermediate layers 124 containing Cu are plated again towards the surface of the side of the 3rd coating 125 in second coating 123, are cooled down,
Obtain titanium-based tin iridium oxide electrode 100 as shown in Figure 3.
Please with reference to Fig. 3 and Fig. 4, party font titanium-based tin iridium oxide electrode 100 includes titanium plate layer 110 and coating
120.Coating 120 in the present embodiment includes first coating 121, second coating 123, the coating 125 of intermediate layer 124 and the 3rd.Its
In, first coating 121 is plated on 110 surface of titanium plate layer, and second coating 123 is plated on first coating 121 away from 110 side of titanium plate layer
Surface, intermediate layer 124 is plated on surface of the second coating 123 away from first coating 121, and it is remote that the 3rd coating 125 is plated on intermediate layer 124
From the surface of the side of second coating 123.
Embodiment 5
Titanium plate is cut into thickness and is the square cards for learning characters shape of 1.5mm, and its surface is polished with sand paper, after then polishing
Titanium plate be immersed in saturation sodium hydroxide solution in boil 45min with oil removing.Then, the titanium plate after oil removing is placed in the of 50 DEG C
Immersion for the first time etches 1.5h in one soak, and it is 1 that first soak contains volume ratio:1.3 nitric acid and hydrochloric acid.Then again
Titanium plate after first time immersion etching is placed in 3.5h is soaked in 85 DEG C of the second soak, the second soak contains volume ratio and is
1:2 sulfuric acid and oxalic acid.
By 4gSnCl4·5H2O and 3gH2IrCl6·6H2It is molten that O is dissolved in the mixing containing 1mL acetic acid and 8mL ethanol solutions
In liquid, presoma masking liquid is obtained.The presoma masking liquid is painted on 110 surface of titanium plate layer, is dried and the under conditions of 400 DEG C
Once sintered 45min, repeats to brush, drying and first sintering 30 times, obtains 25 μm of first coating 121.
Then manganese nitrate solution is painted on surface of the first coating 121 away from titanium plate layer 110, is dried and in 480 DEG C
Under the conditions of second sintering 25min, repeat brushing second coating 123, dry and second sintering 30 times, obtain the second of 50 μm
Coating 123.
By La2O3、Y2O3、Nd2O3And PbO2It is added to the water, and is 2.3 with nitre acid for adjusting pH, obtains acidic Bath.So
Above-mentioned acidic Bath is plated on surface of the second coating 123 away from first coating 121 under conditions of 75 DEG C, repeats to electroplate
10 times, obtain the 3rd coating 125 that thickness is 55 μm.
8 μm of intermediate layers 124 containing Cu are plated again towards the surface of the side of the 3rd coating 125 in second coating 123, are cooled down,
Obtain titanium-based tin iridium oxide electrode 100 as shown in Figure 3.
Please with reference to Fig. 3 and Fig. 4, party font titanium-based tin iridium oxide electrode 100 includes titanium plate layer 110 and coating
120.Coating 120 in the present embodiment includes first coating 121, second coating 123, the coating 125 of intermediate layer 124 and the 3rd.Its
In, first coating 121 is plated on 110 surface of titanium plate layer, and second coating 123 is plated on first coating 121 away from 110 side of titanium plate layer
Surface, intermediate layer 124 is plated on surface of the second coating 123 away from first coating 121, and it is remote that the 3rd coating 125 is plated on intermediate layer 124
From the surface of the side of second coating 123.
Test example
Repeat to implement above-described embodiment 1-5, enough titanium-based tin iridium oxide electrodes are obtained, and respectively by embodiment 1-
The titanium-based tin iridium oxide electrode of 5 gained, is mutually existing together with commercially available common titanium-matrix electrode as a control group as test group 1-5
Under the conditions of reason (i.e. under conditions of voltage 10v), to the organic wastewater of same high salinity, (pH is 3.07, and COD value is
6300mg/L, chlorine ion concentration is 12.1g/L) electrolysis treatment 500min, contrast on after being processed through test group and control group electrolysis
PH value, COD clearances and the chlorion clearance of organic wastewater are stated, its result is as shown in table 1：
PH value, COD clearances and chlorion clearance in the organic wastewater of table 1
| PH value | COD clearances | Chlorion clearance | |
| Test group 1 | 5.9 | 69.3% | 72.5% |
| Test group 2 | 6.5 | 71.1% | 72.7% |
| Test group 3 | 6.9 | 71.7% | 74.9% |
| Test group 4 | 7.2 | 76.4% | 75.2% |
| Test group 5 | 7.5 | 76.6% | 76.9% |
| Control group | 4.8 | 50.4% | 55.7% |
As can be seen from Table 1, under same electrolytic condition, the titanium-based tin iridium oxide electricity that the embodiment of the present invention is prepared
The more existing titanium-matrix electrode in pole is higher to the COD clearances and chlorion clearance in organic wastewater, the organic water after treatment
PH value is raised, illustrate the organic wastewater of the titanium-based tin iridium oxide electrode pair high content of salt that the embodiment of the present invention is prepared with compared with
Good treatment effect, its reason is that titanium-based tin iridium oxide electrode is applied using tin iridium oxide as first in the embodiment of the present invention
Layer, and simultaneously with MnO2As second coating, the electro-catalysis ability of electrode is improve.Contrast test group 1-5, it can be seen that experiment
More preferably, its reason is the titanium-based tin iridium oxygen of the present embodiment to the titanium-based tin iridium oxide Electrode treatment waste water effect that group 5 is prepared
Compound electrode further comprises with La2O3、Y2O3、Nd2O3And PbO2As the 3rd coating and intermediate layer containing Cu elements, and
The thickness of each coating is suitable, and preparation process condition is also more excellent, therefore its treatment effect to organic wastewater is optimal.
In sum, the titanium-based tin iridium oxide electrode of the embodiment of the present invention, with electro-catalysis ability higher, to saliferous
The treatment of organic wastewater has preferable effect；Its preparation method is simple, and easy to operate, cost is relatively low.
Embodiments described above is a part of embodiment of the invention, rather than whole embodiments.Reality of the invention
The detailed description for applying example is not intended to limit the scope of claimed invention, but is merely representative of selected implementation of the invention
Example.Based on the embodiment in the present invention, what those of ordinary skill in the art were obtained under the premise of creative work is not made
Every other embodiment, belongs to the scope of protection of the invention.
Claims (10)
1. a kind of titanium-based tin iridium oxide electrode, it is characterised in that including titanium plate layer, first coating and second coating；Described
One coating is the tin iridium oxide coating for being plated on the titanium plate layer surface, and the second coating is be plated on the first coating remote
From the MnO of the titanium plate one side surface of layer2Coating.
2. titanium-based tin iridium oxide electrode according to claim 1, it is characterised in that the first coating and described second
The thickness of coating is respectively 20-25 μm and 40-60 μm.
3. a kind of preparation method of titanium-based tin iridium oxide electrode, it is characterised in that comprise the following steps：
Titanium plate is polished successively, oil removing, immersion etching, obtain with pitted skin titanium plate layer；
By weight 3-5:2-4 is by SnCl4·5H2O and H2IrCl6·6H2O is dissolved in presoma solvent, obtains presoma painting
Liquid；The presoma masking liquid is painted on the surface of the titanium plate layer, first coating is obtained, the first coating is aoxidized for tin iridium
Thing coating；The presoma solvent be containing volume ratio be 1:The acid solution of 5-10 and the mixed solution of alcoholic solution；
Dry and first coating described in first sintering, manganese nitrate solution is painted on the first coating away from titanium plate layer
The surface of side, obtains second coating, and the second coating is MnO2Coating；
Dry and sinter the second coating for the second time, obtain titanium-based tin iridium oxide electrode.
4. the preparation method of titanium-based tin iridium oxide electrode according to claim 3, it is characterised in that oil removing is to polish
The titanium plate afterwards is immersed in saturation sodium hydroxide solution and boils 40-50min.
5. the preparation method of titanium-based tin iridium oxide electrode according to claim 3, it is characterised in that immersion etching be by
The titanium plate after oil removing is placed in soaks 4-6h in soak, the soak contains in nitric acid, hydrochloric acid, sulfuric acid and oxalic acid extremely
It is few two kinds.
6. the preparation method of titanium-based tin iridium oxide electrode according to claim 5, it is characterised in that immersion etching includes
Immersion etching for the first time, first time immersion etching be by oil removing after the titanium plate be placed in 40-60 DEG C of the first soak
Middle immersion 1-2h, it is 1 that first soak contains volume ratio:The nitric acid and hydrochloric acid of 1-1.5.
7. the preparation method of titanium-based tin iridium oxide electrode according to claim 6, it is characterised in that immersion etching is also wrapped
Second immersion etching is included, second immersion etching is that the titanium plate after first time immersion etching is placed in into 80-90 DEG C
The second soak in soak 3-4h, it is 1 that second soak contains volume ratio:The sulfuric acid and oxalic acid of 1-3.
8. the preparation method of titanium-based tin iridium oxide electrode according to claim 3, it is characterised in that the acid solution
Selected from any one in concentrated hydrochloric acid, citric acid and acetic acid, the alcoholic solution is selected from any in ethanol, isopropanol and ethylene glycol
It is a kind of.
9. the preparation method of titanium-based tin iridium oxide electrode according to claim 3, it is characterised in that first sintering is
At least 25min is sintered under conditions of 350-450 DEG C, second sintering is that 20-30min is sintered under conditions of 450-500 DEG C.
10. the preparation method of the titanium-based tin iridium oxide electrode according to claim any one of 3-9, it is characterised in that
To after the second coating, also including by La2O3、Y2O3And Nd2O3In at least one and PbO2It is added to the water to obtain electroplate liquid, uses
The pH that nitric acid adjusts the electroplate liquid is 2-2.5, acidic Bath is obtained, then to described second under conditions of 70-80 DEG C
Coating is electroplated away from the surface of the first coating, obtains the 3rd coating.
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| CN115159633A (en) * | 2022-07-13 | 2022-10-11 | 杭州奥特新环保科技有限公司 | Method for manufacturing titanium-based iridium tantalum tin coating electrode for high-salt organic wastewater |
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