CN106086989B - A kind of titania modified by Argentine nanotube composite anode and preparation method thereof - Google Patents
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Abstract
The invention discloses a kind of titania modified by Argentine nanotube composite anode, including Titanium base layer, titania nanotube middle layer and active surface layer；Network-like metallic silver is modified in the titania nanotube middle layer.The preparation method of the present invention：First Titanium base is pre-processed；Then Nano tube array of titanium dioxide is grown in Titanium base surface in situ, after cleaning up, by metal modified by silver in nano titania array, the salting liquid for preparing active surface layer is finally coated in the Nano tube array of titanium dioxide surface for being modified with metallic silver, roasting is to get to 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；Metallic silver is modified in Nano tube array of titanium dioxide simultaneously, the ohm voltage drop of titania nanotube middle layer can be reduced, and then reduce the potential of entire composite anode.
Description
Technical field
The invention belongs to electrochemical field more particularly to a kind of titania modified by Argentine nanotube composite anode and its preparations
Method.
Background technology
Metal oxide anode is also known as dimensional stable anode DSA, is invented by H.B.Beer, by Italian De Nora companies head
First realize industrialized production (Ti electrode engineering, Beijing：Metallurgical industry publishing house, 2003), DSA has been widely used for electricity at present
Among metallurgical industry, chlorine industry, plating, wastewater treatment.
French scientist Zwilling V equal to 1999 were reported and two are prepared in titanium plate by anodizing for the first time
The work of titanium oxide nanotubes, anodizing, which has become, till now prepares one of important method of titania nanotube.
Nano-titanium dioxide is as a kind of inorganic functional material, in storage and application, photoelectric conversion, the photocatalytic degradation air of solar energy
And pollutant in water etc. is widely used, and has also obtained Preliminary Applications in terms of the steady Ni―Ti anode of shape.
Although the preparation method of titanium-based composite anode is varied, simple for process, the catalytic activity of coating is high, selectivity
It is good, but there are one it is fatal the shortcomings that：Service life is shorter, and easily passivation forms the very poor titanium dioxide film of one layer of electric conductivity.
Numerous researchers mainly propose following several schemes to solve this technical problem in recent years：The first is applied using heat
Covering increases the method for middle layer, generally stannic oxide middle layer, increases matrix with applying the binding force of interlayer so that entire coating
Densification, and increase the resistance to oxygen in solution, but increase middle layer and only increase coat and base to a certain extent
The physical bond power of body fails fundamentally to stop in solution oxygen from the crack of coating to the erosion of matrix；Second is to adopt
Titanium alloy is formed with titanium and other metals, as applied very extensive titanium manganese alloy, the oxygen on surface inside electrolytic manganese dioxide
Change film be titanium manganese composite oxide, corrosion resistance greatly improves, but the complex manufacturing technology of this method, consistency compared with
Difference；The third is to introduce rare metal Catalytic Layer, but the catalytic action of rare metal can be only applied to specific area, and make
It is excessively high with cost, and titania nanotube middle layer is introduced to increase the resistance to corrosion of electrode, it is this in advance in electrode
Although the method that surface introduces thin fine and close middle layer can greatly increase the service life of Ni―Ti anode, even titanium dioxide
Its electric conductivity of nanotube is still poor, larger so as to cause the pressure drop on entire coating, and energy consumption increases.Therefore, at present
These technical solutions all can not fundamentally solve the short technological deficiency of titanium-based composite anode service life.
Invention content
The technical problems to be solved by the invention are to overcome the shortcomings of to mention in background above technology and defect, provide one
Titania modified by Argentine nanotube composite anode of kind extra long life and preparation method thereof.
In order to solve the above technical problems, technical solution proposed by the present invention is：
A kind of titania modified by Argentine nanotube composite anode, including Titanium base layer, titania nanotube middle layer and
Active surface layer；Network-like metallic silver is modified in the titania nanotube middle layer.
Above-mentioned titania modified by Argentine nanotube composite anode, it is preferred that the active surface layer is SnO2、MnO2、
IrO2、PbO2、RuO2And PdO2One or more of metal oxide mixed layer.
Above-mentioned titania modified by Argentine nanotube composite anode, it is preferred that the Titanium base layer is metallic titanium plate, titanium closes
Gold or titanium thin slice.
The inventive concept total as one, the present invention also provides a kind of systems of titania modified by Argentine nanotube composite anode
Preparation Method includes the following steps：
(1) Titanium base is pre-processed；
(2) using pretreated Titanium base as anode, graphite is put into anodizing solution, anodic oxidation 5 as cathode
~20h makes Titanium base surface in situ grow Nano tube array of titanium dioxide, obtains Titanium base/Nano tube array of titanium dioxide；
(3) it after the Titanium base/Nano tube array of titanium dioxide is cleaned up, immerses in silver nitrate solution, first carries out
Supersound process makes silver nitrate enter in titania nanotube, then carries out thermal decomposition process, the metallic silver for generating thermal decomposition
Modification is in nano titania array；The metallic silver that thermal decomposition generates is attached to grow in titania nanotube tube wall
, full entire titania nanotube is finally filled, forms columnar silver wire, electronics conduction is assumed responsibility in Ni―Ti anode
Effect forms conductive mesh；
(4) one or several kinds in the salting liquid of tin, manganese, iridium, lead, palladium or ruthenium are modified with gold coated in step (3)
Belong to the Nano tube array of titanium dioxide surface of silver, then roasted, obtain the compound sun of titania modified by Argentine nanotube
Pole.
Above-mentioned preparation method, it is preferred that in the step (2), the voltage of anodic oxidation is 30~50V, anodic oxidation
Reaction time is 8~10h.
Above-mentioned preparation method, it is preferred that in the step (3), a concentration of the 0.01 of silver nitrate in silver nitrate solution~
0.03mol/L；The specific process parameter of thermal decomposition process process is：First ultrasound 20~30min, then in air atmosphere, 440~
600 DEG C of roasting temperature 30min.
Above-mentioned preparation method, it is preferred that the pyrolysis processing process repeats 2~3 times.
Above-mentioned preparation method, it is preferred that in the 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 the step (3) refers to be replaced with deionized water and alcohol
Washing is for several times；
Coating and roasting process in the step (4) need to repeat 10~15 times；
In the step (1), the preprocessing process of Titanium base specifically includes：Titanium base is first subjected to sanding and polishing, then right
Titanium base after sanding and polishing is cleaned, and is finally putting into HF and HNO3Mixed acid solution in carry out etch processing.
Compared with prior art, the advantage of the invention is that：
The present invention titania modified by Argentine nanotube composite anode in nanometer titanium dioxide layer be synchronize it is generated in-situ,
Very fine and close, without crack, therefore oxygen that can be effectively in suppression solution directly corrodes Titanium base and makes its passivation, so that
The service life of the composite anode of the present invention is long more than common combination electrode；It is modified in Nano tube array of titanium dioxide simultaneously
There is metallic silver, the ohm voltage drop of titania nanotube middle layer can be reduced, and then reduce the potential of entire composite anode.
Description of the drawings
Fig. 1 is the structure diagram of the titania modified by Argentine nanotube composite anode of the present invention.
Fig. 2 is the scanning electron microscope (SEM) photograph of titania nanotube prepared by the embodiment of the present invention 1.
Fig. 3 is the reinforcing of titania modified by Argentine nanotube composite anode prepared by the embodiment of the present invention 2 and counter electrode
Figure is compared in life test.
Fig. 4 is that titania modified by Argentine nanotube composite anode prepared by the embodiment of the present invention 3 is being electrolysed with counter electrode
Tank voltage compares figure in manganese.
Fig. 5 is that titania modified by Argentine nanotube composite anode prepared by the embodiment of the present invention 4 is being electrolysed with counter electrode
Tank voltage compares figure in manganese.
Specific embodiment
For the ease of understanding the present invention, done more entirely below in conjunction with Figure of description and preferred embodiment to inventing herein
Face meticulously describes, but protection scope of the present invention is not limited to specific examples below.
Unless otherwise defined, all technical terms used hereinafter are generally understood meaning phase with those skilled in the art
Together.Technical term used herein is intended merely to the purpose of description specific embodiment, is not intended to the limitation present invention's
Protection domain.
Unless otherwise specified, various raw material, reagent, the instrument and equipment etc. used in the present invention 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 present invention a kind of, structure diagram is as shown in Figure 1, including titanium
Base layer (Titanium board), titania nanotube middle layer and active surface layer (MnO2Layer), wherein in titania nanotube
Network-like metallic silver is modified in interbed.
The preparation method of the titania modified by Argentine nanotube composite anode of the present embodiment, includes the following steps：
(1) by pure titanium sheet successively with 360#, 600#, 800#, 1000# sand paper sanding and polishing, then respectively with acetone, ethyl alcohol,
Deionized water is respectively cleaned by ultrasonic 10min, then the titanium sheet that surface polishes smooth is put into HF：HNO3=1:In 2 mixed acid solution into
Row activation 30s cleanings, drying；
(2) using step (1) treated pure titanium sheet as anode, graphite as cathode, it is put into anodizing solution (NH4F
11.3g/L, glycerine 250mL, water 250mL) in, temperature is 55 DEG C, voltage is 40V anodic oxygen 8h, in pure titanium sheet
Surface obtains the fine and close titania nanotube that is evenly distributed, and with scanning electron microscopic observation, pattern is as shown in Fig. 2, can from figure
To find out that titania nanotube obtained is neat and fine and close, between 100~200nm, whole surface has very big table in aperture
Area, this can increase subsequent coated weight, increase the compactness of active layer；
(3) by step (2) obtain in the generated in-situ titania nanotube deionized water of pure titanium plate surface and wine
Alternately cleaning three times, is then immersed in prepared 0.01mol/L silver nitrate solutions, then ultrasonic 30min is placed on Muffle essence
It roasts 30min in stove (in air atmosphere) at 500 DEG C, then repeats ultrasound and roasting process 2 times, pass through and thermally decompose what is generated
Silver forms conductive network on nano titanium dioxide pipe；
(4) a concentration of 50% manganese nitrate solution is coated in the titania nanotube surface of step (3) processing, is placed in
15min is roasted in Muffle furnace at 500 DEG C, then repetitive coatings and roasting process 10 times, wherein last time roasting time are
1h is to get to titania modified by Argentine nanotube composite anode.
Using titania modified by Argentine nanotube composite anode manufactured in the present embodiment as anode, using stainless steel as cathode, pole
Away from for 75mm, using industrial electrolysis manganese electrolyte, with 400A/m at 40 DEG C2Electric current carry out electrolysis 20h, anode average potential
For 2.3V, average cell voltage 4.2V.Other impurity elements such as lead are not detected in anode by-product, are synthesized using it as precursor
LiMn2O4 capacity>112mAh/g, cycle life>500 times.
Embodiment 2：
The titania modified by Argentine nanotube composite anode of present invention a kind of, structure diagram is as shown in Figure 1, including titanium
Base layer (Titanium board), titania nanotube middle layer and active surface layer (RuO2Layer), wherein in titania nanotube
Network-like metallic silver is modified in interbed.
The preparation method of the titania modified by Argentine nanotube composite anode of the present embodiment, includes the following steps：
(1) by pure titanium sheet successively with 360#, 600#, 800#, 1000# sand paper sanding and polishing, then respectively with acetone, ethyl alcohol,
Deionized water is respectively cleaned by ultrasonic 10min, then the titanium sheet that surface polishes smooth is put into HF：HNO3=1:In 2 mixed acid solution into
Row activation 30s cleanings, drying；
(2) using step (1) treated pure titanium sheet as anode, graphite as cathode, it is put into anodizing solution (NH4F
11.3g/L, glycerine 250mL, water 250mL) in, temperature is 45 DEG C, voltage is 50V anodic oxygen 10h, in pure titanium sheet
Surface obtains the fine and close titania nanotube that is evenly distributed；
(3) by step (2) obtain in the generated in-situ titania nanotube deionized water of pure titanium plate surface and wine
Alternately cleaning three times, is then immersed in prepared 0.02mol/L silver nitrate solutions, then ultrasonic 30min is placed on Muffle essence
It roasts 30min in stove (in air atmosphere) at 500 DEG C, then repeats ultrasound and roasting process 2 times；
(4) a concentration of 50% nitric acid ruthenium solution is coated in the titania nanotube surface of step (3) processing, is placed in
15min is roasted in Muffle furnace at 500 DEG C, then repetitive coatings and roasting process 10 times, wherein last time roasting time are
1h is to get to titania modified by Argentine nanotube composite anode.
The titania modified by Argentine nanotube composite anode of the present embodiment is done into reinforcing life test in sulfuric acid solution：Make
For comparison, (differed only among titania nanotube using the titanium-based composite anode with being prepared under the same terms of the present invention
The unmodified silver of layer), reinforcing life test has been carried out to two kinds of electrodes, has been obtained as shown in figure 3 as a result, a represents comparison titanium-based
Composite anode, b represent the titania modified by Argentine nanotube composite anode of the present embodiment, by comparing it can be found that this implementation
The service life 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 present invention a kind of, structure diagram is as shown in Figure 1, including titanium
Base layer (Titanium board), titania nanotube middle layer and active surface layer (SnO2Layer), wherein in titania nanotube
Network-like metallic silver is modified in interbed.
The preparation method of the titania modified by Argentine nanotube composite anode of the present embodiment, includes the following steps：
(1) by pure titanium sheet successively with 360#, 600#, 800#, 1000# sand paper sanding and polishing, then respectively with acetone, ethyl alcohol,
Deionized water is respectively cleaned by ultrasonic 10min, then the titanium sheet that surface polishes smooth is put into HF：HNO3=1:In 2 mixed acid solution into
Row activation 30s cleanings, drying；
(2) using step (1) treated pure titanium sheet as anode, graphite as cathode, it is put into anodizing solution (NH4F
11.3g/L, glycerine 250mL, water 250mL) in, temperature is 45 DEG C, voltage is 50V anodic oxygen 10h, in pure titanium sheet
Surface obtains the fine and close titania nanotube that is evenly distributed；
(3) by step (2) obtain in the generated in-situ titania nanotube deionized water of pure titanium plate surface and wine
Alternately cleaning three times, is then immersed in prepared 0.03mol/L silver nitrate solutions, then ultrasonic 30min is placed on Muffle essence
It roasts 30min in stove (in air atmosphere) at 500 DEG C, then repeats ultrasound 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
The solution is coated in the titania nanotube surface of step (3) processing by brush, 20min is then dried at 130 DEG C, then 550
DEG C roasting 20min, this process is repeated 10 times, wherein last time roasts 1h at 550 DEG C to get to titania modified by Argentine nanometer
Pipe composite anode.
Application of the titania modified by Argentine nanotube composite anode of the present embodiment in industrial wastewater：As a comparison, it adopts
(it is unmodified to differ only in titania nanotube middle layer with the titanium-based composite anode with being prepared under the same terms of the present invention
Silver), the phenol that two kinds of electrodes are used to aoxidize in industrial wastewater is tested, has been obtained as shown in Fig. 4 as a result, b represents comparison sun
Pole, a represent titania modified by Argentine nanotube composite anode manufactured in the present embodiment, by comparing it can be found that the present embodiment
The activity of titania modified by Argentine nanotube composite anode greatly improved.
Embodiment 4：
The titania modified by Argentine nanotube composite anode of present invention a kind of, structure diagram is as shown in Figure 1, including titanium
Base layer (Titanium board), titania nanotube middle layer and active surface layer (MnO2Layer), wherein in titania nanotube
Network-like metallic silver is modified in interbed.
The preparation method of the titania modified by Argentine nanotube composite anode of the present embodiment, includes the following steps：
(1) by pure titanium sheet successively with 360#, 600#, 800#, 1000# sand paper sanding and polishing, then respectively with acetone, ethyl alcohol,
Deionized water is respectively cleaned by ultrasonic 10min, then the titanium sheet that surface polishes smooth is put into HF：HNO3=1:In 2 mixed acid solution into
Row activation 30s cleanings, drying；
(2) using step (1) treated pure titanium sheet as anode, graphite as cathode, it is put into anodizing solution (NH4F
11.3g/L, glycerine 250mL, water 250mL) in, temperature is 45 DEG C, voltage is 50V anodic oxygen 10h, in pure titanium sheet
Surface obtains the fine and close titania nanotube that is evenly distributed；
(3) by step (2) obtain in the generated in-situ titania nanotube deionized water of pure titanium plate surface and wine
Alternately cleaning three times, is then immersed in prepared 0.02mol/L silver nitrate solutions, then ultrasonic 30min is placed on Muffle essence
It roasts 30min in stove (in air atmosphere) at 550 DEG C, then repeats ultrasound and roasting process 2 times；
(4) a concentration of 50% manganese nitrate solution is coated in the titania nanotube surface of step (3) processing, is placed in
15min is roasted in Muffle furnace at 500 DEG C, then repetitive coatings and roasting process 10 times, wherein last time roasting time are
1h is to get to titania modified by Argentine nanotube composite anode.
Application of the titania modified by Argentine nanotube composite anode of the present embodiment in electrolytic manganese：As a comparison, it uses
With the titanium-based composite anode (differing only in the unmodified silver of titania nanotube middle layer) prepared under the same terms of the present invention,
Using above-mentioned titania modified by Argentine nanotube composite anode and stainless steel cathode, pole span 75mm, using industrial electrolysis manganese
Electrolyte, with 400A/m at 40 DEG C2Electric current be electrolysed, tank voltage change with time as shown in figure 5, a be this implementation
The tank voltage change curve of the titania modified by Argentine nanotube composite anode of example, b are the tank voltage change curve of counter electrode.
As figure it can be found that the anode tank voltage obtained by the present embodiment is about lower 0.4V than comparison anode tank voltage, and arrives failure voltage 7V
The required time lengthens significantly.
Claims (5)
- A kind of 1. preparation method of titania modified by Argentine nanotube composite anode, which is characterized in that the modified titanium dioxide of silver Titanium nanotube composite anode includes Titanium base layer, titania nanotube middle layer and active surface layer；The titanium dioxide is received Network-like metallic silver is modified in mitron middle layer, wherein the active surface layer is SnO2、MnO2、IrO2、RuO2With PdO2One or more of metal oxide mixed layer；The preparation method packet of the titania modified by Argentine nanotube composite anode Include following steps：(1) Titanium base is pre-processed；(2) using pretreated Titanium base as anode, graphite is put into anodizing solution as cathode, and 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) it after the Titanium base/Nano tube array of titanium dioxide is cleaned up, immerses in silver nitrate solution, is surpassed successively Sound, thermal decomposition process make the metal modified by silver that thermal decomposition generates in nano titania array；Silver nitrate in silver nitrate solution A concentration of 0.01~0.03mol/L；The specific process parameter of thermal decomposition process process is：First ultrasound 20~30min, Ran Houkong In gas atmosphere, 440~600 DEG C of roasting temperature 30min；Thermal decomposition process process repeats 2~3 times；(4) one or several kinds in the salting liquid of tin, manganese, iridium, palladium or ruthenium are modified with the two of metallic silver coated in step (3) Titania nanotube array surface, is then roasted, and obtains the titania modified by Argentine nanotube composite anode.
- 2. preparation method as described in claim 1, which is characterized in that in the step (2), the voltage of anodic oxidation for 30~ 50V, anodic oxidation reactions time are 8~10h.
- 3. preparation method as described in claim 1, which is characterized in that in the step (3), the temperature of thermal decomposition process roasting It is 500~550 DEG C.
- 4. preparation method as described in claim 1, which is characterized in that the cleaning process in the step (3) refer to spend from Sub- water and alcohol alternately wash for several times；Coating and roasting process in the step (4) need to repeat 10~15 times；In the step (1), the preprocessing process of Titanium base specifically includes：Titanium base is first subjected to sanding and polishing, then to polishing Titanium base after polishing is cleaned, and is finally putting into HF and HNO3Mixed acid solution in carry out etch processing.
- 5. preparation method as described in claim 1, which is characterized in that the Titanium base layer is layer of titanium metal or titanium alloy layer.
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| CN109534460B (en) * | 2018-12-25 | 2021-11-23 | 广东省稀有金属研究所 | Titanium electrode and preparation method and application thereof |
| EP4083275A1 (en) * | 2021-04-30 | 2022-11-02 | Fundació Institut Catala de Recerca de l'Aigua (ICRA) | Method to prepare an electrode with a manganese oxide coated titanium oxide nanotube array interlayer, electrode obtained thereof, and uses of the electrode |
| CN113402111A (en) * | 2021-06-03 | 2021-09-17 | 哈尔滨工程大学 | Biological/photoelectric/solar coupling sewage treatment integrated device |
| CN114242981B (en) * | 2021-12-17 | 2024-04-09 | 太原理工大学 | TiO (titanium dioxide) 2 -SnO 2 Composite material, preparation method and application thereof |
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