CN106086989A - A kind of titania modified by Argentine nanotube composite anode and preparation method thereof - Google Patents

A kind of titania modified by Argentine nanotube composite anode and preparation method thereof Download PDF

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CN106086989A
CN106086989A CN201610573885.3A CN201610573885A CN106086989A CN 106086989 A CN106086989 A CN 106086989A CN 201610573885 A CN201610573885 A CN 201610573885A CN 106086989 A CN106086989 A CN 106086989A
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titania
modified
argentine
titanium
composite anode
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CN106086989B (en
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郭华军
罗树亮
李星海
王志兴
彭文杰
胡启阳
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Central South University
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    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
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    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
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    • C25C1/00—Electrolytic production, recovery or refining of metals by electrolysis of solutions
    • C25C1/06—Electrolytic production, recovery or refining of metals by electrolysis of solutions or iron group metals, refractory metals or manganese
    • C25C1/10—Electrolytic production, recovery or refining of metals by electrolysis of solutions or iron group metals, refractory metals or manganese of chromium or manganese
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
    • C25C7/00—Constructional parts, or assemblies thereof, of cells; Servicing or operating of cells
    • C25C7/02—Electrodes; Connections thereof
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00—Nature of the contaminant
    • C02F2101/30—Organic compounds
    • C02F2101/34—Organic compounds containing oxygen
    • C02F2101/345—Phenols
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    • 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

Abstract

The invention discloses a kind of titania modified by Argentine nanotube composite anode, including Titanium base layer, titania nanotube intermediate layer and active surface layer；Described titania nanotube intermediate layer is modified with network-like argent.The preparation method of the present invention: first Titanium base is carried out pretreatment；Then Nano tube array of titanium dioxide is grown at Titanium base surface in situ, after cleaning up, argent is modified in nano titania array, finally the saline solution of preparation active surface layer is coated in the Nano tube array of titanium dioxide surface being modified with argent, roasting, i.e. obtains titania modified by Argentine nanotube composite anode.The service life of the titania modified by Argentine nanotube composite anode of the present invention is long more than common combination electrode；It is modified with argent at Nano tube array of titanium dioxide simultaneously, the ohm voltage drop in titania nanotube intermediate layer can be reduced, and then reduce the electromotive force of whole composite anode.

Description

A kind of titania modified by Argentine nanotube composite anode and preparation method thereof
Technical field
The invention belongs to electrochemical field, particularly relate to a kind of titania modified by Argentine nanotube composite anode and preparation thereof Method.
Background technology
Metal oxide anode is also called dimensional stable anode DSA, H.B.Beer invent, first by De Nora company of Italy First realizing industrialized production (Ti electrode engineering, Beijing: metallurgical industry publishing house, 2003), current DSA has been widely used for electricity Among metallurgical industry, chlorine industry, plating, waste water process.
French scientist Zwilling V prepares two by anodizing equal to reported first in 1999 on titanium plate The work of titanium oxide nanotubes, anodizing has become as and prepares one of important method of titania nanotube till now. Nano titanium oxide is as a kind of inorganic functional material, at storage and application, photoelectric conversion, the photocatalytic degradation air of solar energy And the aspect such as pollutant in water is widely used, and have also been obtained Preliminary Applications in terms of the steady Ni-Ti anode of shape.
Although the preparation method of titanio composite anode is varied, technique is simple, and the catalysis activity of coating is high, selectivity Good, but there is a fatal shortcoming: and service life is shorter, and easily passivation forms the titanium dioxide film that one layer of electric conductivity is very poor. The most numerous researcheres, in order to solve this technical problem, mainly propose following several scheme: the first is to use heat to be coated with Cover the method increasing intermediate layer, generally tin ash intermediate layer, increase matrix and the adhesion being coated with interlayer so that whole coating Densification, and increase the resistance of oxygen in solution, but be to increase intermediate layer and simply add coat and base to a certain extent The physical bond power of body, fails fundamentally to stop the erosion to matrix from the crack of coating of oxygen in solution；The second is to adopt Titanium alloy is formed with other metal, as applied quite varied titanium manganese alloy, the oxygen on its surface inside electrolytic manganese dioxide with titanium Changing film is titanium manganese composite oxide, and its corrosion resistance is greatly improved, but the complex manufacturing technology of this method, and concordance is relatively Difference；The third is introduced into rare metal Catalytic Layer, but the catalytic action of rare metal can be only applied to specific area, and makes With high cost, and introduce titania nanotube intermediate layer to increase the resistance to corrosion of electrode, this in advance at electrode Although surface introduces the method in thin fine and close intermediate layer and can be greatly increased the service life of Ni-Ti anode, but even titanium dioxide Its electric conductivity of nanotube is the most poor, thus causes the pressure drop on whole coating relatively big, and energy consumption increases.Therefore, current These technical schemes all cannot fundamentally solve short technological deficiency in titanio composite anode service life.
Summary of the invention
The technical problem to be solved is, overcomes the deficiency and defect mentioned in background above technology, it is provided that one Plant titania modified by Argentine nanotube composite anode of extra long life and preparation method thereof.
For solving above-mentioned technical problem, the technical scheme that the present invention proposes is:
A kind of titania modified by Argentine nanotube composite anode, including Titanium base layer, titania nanotube intermediate layer and Active surface layer；Described titania nanotube intermediate layer is modified with network-like argent.
Above-mentioned titania modified by Argentine nanotube composite anode, it is preferred that described active surface layer is SnO2、MnO2、 IrO2、PbO2、RuO2And PdO2In one or more metal-oxide mixed layers.
Above-mentioned titania modified by Argentine nanotube composite anode, it is preferred that described Titanium base layer is metallic titanium plate, titanium conjunction Gold or titanium thin slice.
As a total inventive concept, the present invention also provides for the system of a kind of titania modified by Argentine nanotube composite anode Preparation Method, comprises the following steps:
(1) Titanium base is carried out pretreatment；
(2) using pretreated Titanium base as anode, graphite, as negative electrode, is put in anodizing solution, anodic oxidation 5 ～20h, make Titanium base surface in situ grow Nano tube array of titanium dioxide, obtain Titanium base/Nano tube array of titanium dioxide；
(3), after described Titanium base/Nano tube array of titanium dioxide being cleaned up, immerse in silver nitrate solution, first carry out Supersound process makes silver nitrate enter in titania nanotube, then carries out thermal decomposition process, makes the argent that thermal decomposition produces Modify in nano titania array；The argent that thermal decomposition produces is attached to grow in titania nanotube tube wall , finally fill full whole titania nanotube, shape pillared silver wire, it assume responsibility for electronics conduction in Ni-Ti anode Effect, forms conductive mesh；
(4) one or several in the saline solution of stannum, manganese, iridium, lead, palladium or ruthenium are coated in step (3) and are modified with gold Belong to the Nano tube array of titanium dioxide surface of silver, then carry out roasting, obtain the compound sun of described titania modified by Argentine nanotube Pole.
Above-mentioned preparation method, it is preferred that in described step (2), anodised voltage is 30～50V, anodic oxidation Response time is 8～10h.
Above-mentioned preparation method, it is preferred that in described step (3), in silver nitrate solution the concentration of silver nitrate be 0.01～ 0.03mol/L；The concrete technology parameter of thermal decomposition process process is: first ultrasonic 20～30min, then in air atmosphere, 440～ 600 DEG C of roasting temperature 30min.
Above-mentioned preparation method, it is preferred that described pyrolysis processing process repeats 2～3 times.
Above-mentioned preparation method, it is preferred that in described step (3), the temperature of thermal decomposition process roasting is 500～550 DEG C.
Above-mentioned preparation method, it is preferred that the cleaning process in described step (3) refers to replace with deionized water and ethanol Washing is for several times；
Coating and roasting process in described step (4) need to repeat 10～15 times；
In described step (1), the preprocessing process of Titanium base specifically includes: first Titanium base is carried out sanding and polishing, more right Titanium base after sanding and polishing is carried out, and is finally putting into HF and HNO3Mixed acid solution in carry out etch process.
Compared with prior art, it is an advantage of the current invention that:
In the titania modified by Argentine nanotube composite anode of the present invention, nanometer titanium dioxide layer is that synchronization is generated in-situ, The finest and close, there is no crack, therefore effectively directly can corrode Titanium base and make it be passivated by the oxygen in suppression solution, so that The service life of the composite anode of the present invention is long more than common combination electrode；Modify in Nano tube array of titanium dioxide simultaneously There is argent, the ohm voltage drop in titania nanotube intermediate layer can be reduced, and then reduce the electromotive force of whole composite anode.
Accompanying drawing explanation
Fig. 1 is the structural representation of the titania modified by Argentine nanotube composite anode of the present invention.
Fig. 2 is the scanning electron microscope (SEM) photograph of the titania nanotube of the embodiment of the present invention 1 preparation.
Fig. 3 is the titania modified by Argentine nanotube composite anode strengthening with counter electrode of the embodiment of the present invention 2 preparation Life test comparison diagram.
Fig. 4 is that the titania modified by Argentine nanotube composite anode of the embodiment of the present invention 3 preparation is being electrolysed with counter electrode Tank voltage comparison diagram in manganese.
Fig. 5 is that the titania modified by Argentine nanotube composite anode of the embodiment of the present invention 4 preparation is being electrolysed with counter electrode Tank voltage comparison diagram in manganese.
Detailed description of the invention
For the ease of understanding the present invention, below in conjunction with Figure of description and preferred embodiment, invention herein is done more complete Face, describe meticulously, but protection scope of the present invention is not limited to specific examples below.
Unless otherwise defined, all technical term used hereinafter is generally understood that implication phase with those skilled in the art With.Technical term used herein is intended merely to describe the purpose of specific embodiment, is not intended to limit the present invention's Protection domain.
Unless otherwise specified, the various raw materials used in the present invention, reagent, instrument and equipment etc. all can pass through city Field is commercially available or can be prepared by existing method.
Embodiment 1:
The titania modified by Argentine nanotube composite anode of a kind of present invention, its structural representation is as it is shown in figure 1, include titanium Base layer (Titanium board), titania nanotube intermediate layer and active surface layer (MnO2Layer), wherein in titania nanotube Interbed is modified with network-like argent.
The preparation method of the titania modified by Argentine nanotube composite anode of the present embodiment, comprises the following steps:
(1) by pure titanium sheet successively with 360#, 600#, 800#, 1000# sand papering polish, more respectively with acetone, ethanol, Deionized water each ultrasonic cleaning 10min, then the titanium sheet polished smooth on surface puts into HF:HNO3The mixed acid solution of=1:2 enters Row activation 30s cleans, and dries；
(2) the pure titanium sheet after processing using step (1), as anode, graphite as negative electrode, puts into anodizing solution (NH4F 11.3g/L, glycerol 250mL, water 250mL) in, temperature be 55 DEG C, voltage be 40V anodic oxygen 8h, in pure titanium sheet Surface obtains being evenly distributed the titania nanotube of densification, and with scanning electron microscopic observation, its pattern is as in figure 2 it is shown, can from figure To find out that prepared titania nanotube is neatly fine and close, aperture is between 100～200nm, and there is the biggest table on whole surface Area, this can increase follow-up coated weight, increase the compactness of active layer；
(3) step (2) is obtained at pure titanium plate surface generated in-situ titania nanotube deionized water and wine Essence is alternately cleaned three times, is then immersed in the 0.01mol/L silver nitrate solution prepared, ultrasonic 30min, is then placed on Muffle In stove at 500 DEG C roasting 30min (in air atmosphere), then repeat ultrasonic and roasting process 2 times, produced by thermal decomposition Silver forms conductive network on nano titanium dioxide pipe；
(4) manganese nitrate solution that concentration is 50% is coated in the titania nanotube surface that step (3) processes, is placed in In Muffle furnace at 500 DEG C roasting 15min, then repetitive coatings and roasting process 10 times, wherein last roasting time is 1h, i.e. obtains titania modified by Argentine nanotube composite anode.
The titania modified by Argentine nanotube composite anode prepared with the present embodiment as anode, with rustless steel as negative electrode, pole Away from for 75mm, use industrial electrolysis manganese electrolyte, with 400A/m at 40 DEG C2Electric current carry out be electrolysed 20h, anode average potential For 2.3V, average cell voltage is 4.2V.Anode by-product is not detected by other impurity elements such as lead, with for precursor synthesize LiMn2O4 capacity > 112mAh/g, cycle life > 500 times.
Embodiment 2:
The titania modified by Argentine nanotube composite anode of a kind of present invention, its structural representation is as it is shown in figure 1, include titanium Base layer (Titanium board), titania nanotube intermediate layer and active surface layer (RuO2Layer), wherein in titania nanotube Interbed is modified with network-like argent.
The preparation method of the titania modified by Argentine nanotube composite anode of the present embodiment, comprises the following steps:
(1) by pure titanium sheet successively with 360#, 600#, 800#, 1000# sand papering polish, more respectively with acetone, ethanol, Deionized water each ultrasonic cleaning 10min, then the titanium sheet polished smooth on surface puts into HF:HNO3The mixed acid solution of=1:2 enters Row activation 30s cleans, and dries；
(2) the pure titanium sheet after processing using step (1), as anode, graphite as negative electrode, puts into anodizing solution (NH4F 11.3g/L, glycerol 250mL, water 250mL) in, temperature be 45 DEG C, voltage be 50V anodic oxygen 10h, in pure titanium sheet Surface obtains the fine and close titania nanotube that is evenly distributed；
(3) step (2) is obtained at pure titanium plate surface generated in-situ titania nanotube deionized water and wine Essence is alternately cleaned three times, is then immersed in the 0.02mol/L silver nitrate solution prepared, ultrasonic 30min, is then placed on Muffle In stove at 500 DEG C roasting 30min (in air atmosphere), then repeat ultrasonic and roasting process 2 times；
(4) the nitric acid ruthenium solution that concentration is 50% is coated in the titania nanotube surface that step (3) processes, is placed in In Muffle furnace at 500 DEG C roasting 15min, then repetitive coatings and roasting process 10 times, wherein last roasting time is 1h, i.e. obtains titania modified by Argentine nanotube composite anode.
The titania modified by Argentine nanotube composite anode of the present embodiment is done strengthening life test in sulfuric acid solution: make For contrast, use and (differ only in the middle of titania nanotube with the titanio composite anode of preparation under the same terms of the present invention Layer unmodified silver), two kinds of electrodes are carried out reinforcing life test, obtains result as shown in figure 3, a represents contrast titanio Composite anode, b represents the titania modified by Argentine nanotube composite anode of the present embodiment, by contrast it is found that this enforcement The life-span of the titania modified by Argentine nanotube composite anode of example is greatly improved.
Embodiment 3:
The titania modified by Argentine nanotube composite anode of a kind of present invention, its structural representation is as it is shown in figure 1, include titanium Base layer (Titanium board), titania nanotube intermediate layer and active surface layer (SnO2Layer), wherein in titania nanotube Interbed is modified with network-like argent.
The preparation method of the titania modified by Argentine nanotube composite anode of the present embodiment, comprises the following steps:
(1) by pure titanium sheet successively with 360#, 600#, 800#, 1000# sand papering polish, more respectively with acetone, ethanol, Deionized water each ultrasonic cleaning 10min, then the titanium sheet polished smooth on surface puts into HF:HNO3The mixed acid solution of=1:2 enters Row activation 30s cleans, and dries；
(2) the pure titanium sheet after processing using step (1), as anode, graphite as negative electrode, puts into anodizing solution (NH4F 11.3g/L, glycerol 250mL, water 250mL) in, temperature be 45 DEG C, voltage be 50V anodic oxygen 10h, in pure titanium sheet Surface obtains the fine and close titania nanotube that is evenly distributed；
(3) step (2) is obtained at pure titanium plate surface generated in-situ titania nanotube deionized water and wine Essence is alternately cleaned three times, is then immersed in the 0.03mol/L silver nitrate solution prepared, ultrasonic 30min, is then placed on Muffle In stove at 500 DEG C roasting 30min (in air atmosphere), then repeat ultrasonic and roasting process 2 times；
(4) stannic chloride pentahydrate is dissolved in the polybenzazole precursor liquid solution obtained by citric acid and ethylene glycol, with hair This solution is coated in the titania nanotube surface that step (3) processes by brush, then dries 20min at 130 DEG C, then 550 DEG C roasting 20min, this process is repeated 10 times, wherein last at 550 DEG C of roasting 1h, i.e. obtains titania modified by Argentine nanometer Pipe composite anode.
The titania modified by Argentine nanotube composite anode of the present embodiment application in industrial wastewater: as a comparison, adopt (titania nanotube intermediate layer unmodified is differed only in with the titanio composite anode of preparation under the same terms of the present invention Silver), two kinds of electrodes are used for the phenol test aoxidizing in industrial wastewater, have obtained the shown result such as Fig. 4, b represents contrast sun Pole, a represents titania modified by Argentine nanotube composite anode prepared by the present embodiment, by contrast it is found that the present embodiment The activity of titania modified by Argentine nanotube composite anode be greatly improved.
Embodiment 4:
The titania modified by Argentine nanotube composite anode of a kind of present invention, its structural representation is as it is shown in figure 1, include titanium Base layer (Titanium board), titania nanotube intermediate layer and active surface layer (MnO2Layer), wherein in titania nanotube Interbed is modified with network-like argent.
The preparation method of the titania modified by Argentine nanotube composite anode of the present embodiment, comprises the following steps:
(1) by pure titanium sheet successively with 360#, 600#, 800#, 1000# sand papering polish, more respectively with acetone, ethanol, Deionized water each ultrasonic cleaning 10min, then the titanium sheet polished smooth on surface puts into HF:HNO3The mixed acid solution of=1:2 enters Row activation 30s cleans, and dries；
(2) the pure titanium sheet after processing using step (1), as anode, graphite as negative electrode, puts into anodizing solution (NH4F 11.3g/L, glycerol 250mL, water 250mL) in, temperature be 45 DEG C, voltage be 50V anodic oxygen 10h, in pure titanium sheet Surface obtains the fine and close titania nanotube that is evenly distributed；
(3) step (2) is obtained at pure titanium plate surface generated in-situ titania nanotube deionized water and wine Essence is alternately cleaned three times, is then immersed in the 0.02mol/L silver nitrate solution prepared, ultrasonic 30min, is then placed on Muffle In stove at 550 DEG C roasting 30min (in air atmosphere), then repeat ultrasonic and roasting process 2 times；
(4) manganese nitrate solution that concentration is 50% is coated in the titania nanotube surface that step (3) processes, is placed in In Muffle furnace at 500 DEG C roasting 15min, then repetitive coatings and roasting process 10 times, wherein last roasting time is 1h, i.e. obtains titania modified by Argentine nanotube composite anode.
The titania modified by Argentine nanotube composite anode of the present embodiment application in electrolytic manganese: as a comparison, uses With the titanio composite anode (differ only in titania nanotube intermediate layer unmodified silver) of preparation under the same terms of the present invention, Using above-mentioned titania modified by Argentine nanotube composite anode and stainless steel cathode, pole span is 75mm, uses industrial electrolysis manganese Electrolyte, with 400A/m at 40 DEG C2Electric current be electrolysed, tank voltage is over time as it is shown in figure 5, a is this enforcement The tank voltage change curve of the titania modified by Argentine nanotube composite anode of example, b is the tank voltage change curve of counter electrode. By figure it appeared that the anode slot voltage ratio the lowest 0.4V of counter electrode tank voltage of the present embodiment gained, and to failure voltage 7V The required time lengthens significantly.

Claims (9)

1. a titania modified by Argentine nanotube composite anode, it is characterised in that described titania modified by Argentine nanotube is multiple Heyang pole includes Titanium base layer, titania nanotube intermediate layer and active surface layer；Described titania nanotube intermediate layer In be modified with network-like argent.
2. titania modified by Argentine nanotube composite anode as claimed in claim 1, it is characterised in that described active surface layer For SnO2、MnO2、IrO2、PbO2、RuO2And PdO2In one or more metal-oxide mixed layers.
3. titania modified by Argentine nanotube composite anode as claimed in claim 1, it is characterised in that described Titanium base layer is Metallic titanium plate, titanium alloy or titanium thin slice.
4. the preparation method of a titania modified by Argentine nanotube composite anode, it is characterised in that comprise the following steps:
(1) Titanium base is carried out pretreatment；
(2) using pretreated Titanium base as anode, graphite, as negative electrode, is put in anodizing solution, anodic oxidation 5～ 20h, makes Titanium base surface in situ grow Nano tube array of titanium dioxide, obtains Titanium base/Nano tube array of titanium dioxide；
(3), after described Titanium base/Nano tube array of titanium dioxide being cleaned up, immerse in silver nitrate solution, surpass successively Sound, thermal decomposition process, the argent making thermal decomposition produce is modified in nano titania array；
(4) one or several in the saline solution of stannum, manganese, iridium, lead, palladium or ruthenium are coated in step (3) and are modified with argent Nano tube array of titanium dioxide surface, then carry out roasting, obtain described titania modified by Argentine nanotube composite anode.
5. preparation method as claimed in claim 4, it is characterised in that in described step (2), anodised voltage be 30～ 50V, the anodic oxidation reactions time is 8～10h.
6. preparation method as claimed in claim 4, it is characterised in that in described step (3), silver nitrate in silver nitrate solution Concentration is 0.01～0.03mol/L；The concrete technology parameter of thermal decomposition process process is: first ultrasonic 20～30min, then air In atmosphere, 440～600 DEG C of roasting temperature 30min.
7. preparation method as claimed in claim 6, it is characterised in that described thermal decomposition process process repeats 2～3 times.
8. preparation method as claimed in claim 6, it is characterised in that in described step (3), the temperature of thermal decomposition process roasting It it is 500～550 DEG C.
9. preparation method as claimed in claim 4, it is characterised in that the cleaning process in described step (3) refer to spend from The alternately washing of sub-water and ethanol is for several times；
Coating and roasting process in described step (4) need to repeat 10～15 times；
In described step (1), the preprocessing process of Titanium base specifically includes: first Titanium base is carried out sanding and polishing, then to polishing Titanium base after polishing is carried out, and is finally putting into HF and HNO3Mixed acid solution in carry out etch process.
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