CN104593818B - Titanium-based composite anode as well as preparation method and application thereof - Google Patents
Titanium-based composite anode as well as preparation method and application thereof Download PDFInfo
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Abstract
The invention provides a titanium-based composite anode as well as a preparation method and application of the titanium-based composite anode. The titanium-based composite anode comprises a titanium substrate, a double-dense protection intermediate layer and an active surface layer, wherein the double-dense protection intermediate layer is divided into two layers including a titanium dioxide nanotube layer and an antimony-tin oxide dense layer; a honeycomb-shaped antimony-tin oxide layer also covers the antimony-tin oxide dense layer. An electrode is long in service life, high in electrocatalytic activity and relatively high in efficiency of oxygenolysis of organic matters in sewage treatment, and can be applied to sewage treatment and chlor-alkali industry.
Description
Technical field
The present invention relates to electrochemical field, more particularly to a kind of composite anode and its preparation method and application.
Background technology
Titanio composite anode is the metal oxidation that Sb, Ir, Sn, Mn isoreactivity element is coated based on titanium or titanium alloy
The electrode that thing is constituted, it is high with catalysis activity, delay matrix to be passivated, the advantages of the selectivity of reaction is preferable.Traditional electrode, such as
Graphite anode intensity is not high, and lead silver alloy anode has lead and dissolves the shortcomings of entering electrolyte.Titanio composite anode can basis
The different purposes of electrode and requirement, are targetedly designed the coating and structure of electrode, and with this side reaction is reduced
Occur, improve the yield and current efficiency of target product.This titanio composite anode is widely used in manganese electrolytic industry, chlor-alkali work
The fields such as industry, sewage disposal.
The preparation method of titanio composite anode mainly has thermal decomposition method, sol-gel process, magnetron sputtering method, electrochemistry to sink
The methods such as area method, it is different that different preparation methoies is obtained the structure and activity of coating, and electrochemical deposition method is obtained to be applied
Layer it is fine and close thus its last a long time, coating catalysis activity is higher obtained in thermal decomposition method.But also can adjust component
Ratio come adjust coating activity and structure.Therefore preferable coating proportion of composing, sintering temperature can be determined according to experiment
The higher titanio composite anode of activity is prepared with a series of electrolytic condition.
Although the preparation method of titanio composite anode is varied, process is simple, the catalysis activity of coating is high, selectivity
It is good, but have the shortcomings that one it is fatal：Service life is shorter.In recent years numerous researcheres are in order to solve this problem, it is proposed that
Many schemes, did many experiments.The main cause of electrode inactivation is that Titanium base is oxidized, and Titanium base Surface Creation one layer is blunt
Change film, or active substance comes off or is dissolved.The oxide of Sn, Sb such as Shi Yanhua as intermediate layer, strengthen active layer and
The adhesion of matrix, and delay passivation (Effect of SbO of the oxygen to matrixx +SnO2 Intermediate Layer
on the Properties of Ti-based MnO2 Anode[J].Acta Phys. Chim. Sin.,2007,23
(10):1553-1559.), but it has also been found that the intermediate layer for preparing and active layer are all not fine and close enough, delay what oxygen was passivated to matrix
Action effect is still not ideal enough.Increasing the content in intermediate layer can reduce oxygen evolution potential, and this application to titanio composite anode is
Unfavorable, such as during sewage is processed, oxygen evolution potential is low to be unfavorable for that Organic substance is oxidized anodically and is beneficial to precipitated oxygen, from
And reduce current efficiency.
The content of the invention
The technical problem to be solved is to overcome the shortcomings of to be mentioned and defect in background above technology, there is provided one
Plant long service life, the good titanio composite anode of electro catalytic activity and its preparation method and application.
To solve above-mentioned technical problem, technical scheme proposed by the present invention is a kind of titanio composite anode, and the titanio is combined
Anode includes Titanium base, double fine and close protection intermediate layers, active surface layer；Double fine and close protection intermediate layer is divided into two-layer, and first
Layer is titania nanotube, and the second layer is tin-antimony oxide compacted zone；Honeycomb is covered with the tin-antimony oxide compacted zone again
Shape tin-antimony oxide layer.
Above-mentioned titanio composite anode, it is preferred that the Titanium base is metallic titanium plate, titanium alloy or titanium thin slice；The work
Property surface layer is MnO2、IrO2、Ta2O5、RuO2In one or more mixed-metal oxides.
As a total inventive concept, present invention also offers a kind of preparation method of above-mentioned titanio composite anode,
Comprise the following steps：
（1）By Titanium base polishing, alkali cleaning or pickling, the Titanium base of clean surface is obtained；
（2）The preparation in double fine and close protection intermediate layers：
The preparation of titania nanotube：Using through the Titanium base of above-mentioned process as anode, graphite electrode as negative electrode,
It is electrolysed in the alcohols electrolyte containing NaF, then Titanium base is carried out into roasting, is obtained the electricity containing titania nanotube
Pole；
The preparation of tin-antimony oxide compacted zone：Citric acid and ethylene glycol are mixed, reacting by heating is subsequently adding pink salt and antimony
Salt, reacting by heating prepares polybenzazole precursor liquid solution, and above-mentioned polybenzazole precursor liquid solution is coated in into above-mentioned electrode table
Face, roasting, this process repeats 10 ~ 15 times, obtains the electrode containing the tin-antimony oxide compacted zone；
（3）Cellular tin-antimony oxide layer：Above-mentioned electrode is infiltrated in polymethyl methacrylate liquid, drying is obtained
The electrode of the gluey crystallization template of polymethyl methacrylate is covered with to surface；
Addition phenol-formaldehyde polymer precursor solution after stirring, adds in the ethanol solution containing pink salt and antimonic salt
Plus polypropylene glycol and the addition polymers of oxirane, stir, target liquid is obtained, above-mentioned electrode is immersed in above-mentioned target liquid,
Roasting after drying, you can the electrode containing cellular tin-antimony oxide layer is obtained；
（4）The preparation of active surface layer：One or more in manganese, iridium, tantalum or ruthenium saline solution are coated in into above-mentioned electrode
Surface, roasting, this process repeats 10 ~ 15 times；One kind for being then coated with the manganese containing fiber, iridium, tantalum or ruthenium saline solution or
Several, roasting, this process repeats 4 ~ 8 times, that is, obtain the titanio composite anode.
The present invention prepares layer of titanium dioxide and receives by anode oxidation method, between matrix and tin-antimony oxide compacted zone
Mitron, by the service life for improving the binding ability of intermediate layer and substrate so as to improve electrode, moreover it is possible to ensure electrode have compared with
Good catalysis activity.The present invention also by template, in double fine and close protection interlayer surfaces one layer of cellular stannum antimony oxygen is prepared for
Compound, improves the specific surface area in intermediate layer, to strengthen the binding ability in intermediate layer and active surface layer, it is suppressed that surface activity
Coming off for layer, extends the life-span of electrode.Appropriate cellulose is added in manganese, iridium, tantalum or ruthenium saline solution, is increased by pore-creating
The specific surface area of active layer, the catalytic reaction to occur on surface provides more reactivity points, so as to improve electrode
Catalytic capability.
In above-mentioned preparation method, it is preferred that the electrode is infiltrated in polymethyl methacrylate liquid post-drying
Temperature is 70 DEG C, and the time is 24h；It it is 90 ~ 110 DEG C by the temperature that the electrode immerses the target liquid post-drying, the time is 0.5
~ 3h, this process repeats 3 ~ 5 times；The step（2）It is middle to add after the citric acid and ethylene glycol, the temperature of reacting by heating is 55 ~
65 DEG C, after adding the pink salt and antimonic salt, the temperature of reacting by heating is 85 ~ 95 DEG C；The step（2）、（4）In roasting temperature
Spend for 450 DEG C ~ 550 DEG C, the time is 30min ~ 180min；
The step（3）The process conditions of middle roasting are：In an ar atmosphere, 1 ~ 4h of roasting, Ran Hou at 400 ~ 480 DEG C
2 ~ 5h of roasting at 780 ~ 850 DEG C, heating rate is controlled in 1 ~ 2 DEG C/min.
In above-mentioned preparation method, it is preferred that the time of the electrolysis be 1h ~ 6h, the water content control of electrolyte during electrolysis
Between 1g/L ~ 10g/L, voltage is controlled between 15V ~ 75V system.
In above-mentioned preparation method, it is preferred that the step（2）With step（3）In pink salt be SnCl4·5H2O, antimonic salt
For SbCl3；Wherein step（2）Middle citric acid, ethylene glycol, pink salt, the mol ratio of antimonic salt are 1: 4: 0 ~ 0.5: 0 ~ 0.1.Above-mentioned
In preparation method, it is preferred that the preparation of the polymethyl methacrylate liquid is comprised the following steps：Respectively with sodium hydroxide and
Deionized water washs methyl methacrylate three times, then by following weight portion and parts by volume addition raw material：7 ~ 15 weight portions
Methyl methacrylate；90 ~ 200 parts by volume deionized waters；7 ~ 15 weight portion K2S2O8；In 50 ~ 90 DEG C and nitrogen after mix homogeneously
5 ~ 9h is reacted under atmosphere, is filtered, removed and be obtained after aggregate polymethyl methacrylate (PMMA) liquid；
The unit ratio corresponding relation of the weight portion and parts by volume is g/ml.
In above-mentioned preparation method, it is preferred that the preparation of the phenol-formaldehyde polymer precursor solution includes following step
Suddenly：The phenol of 3 ~ 9 weight portions and sodium hydroxide solution that 0.2 ~ 3 weight portion, mass fraction are 20% are mixed and stirred for, then
8 ~ 14 parts by weight of formaldehyde are added, 1h is stirred at 60 ~ 80 DEG C, after being cooled to room temperature, with 1 ~ 4mol L-1Hydrochloric acid by the pH of solution
5 ~ 8 are adjusted to, then distill solution, then dissolved with a certain amount of ethanol, sodium chloride crystal unnecessary in solution is filtered
Remove, the i.e. described phenol-formaldehyde polymer precursor solution of filtrate.
In above-mentioned preparation method, it is preferred that the manganese, iridium, tantalum or ruthenium salt are respectively Mn (NO3)2、IrCl3、TaCl5、
RuCl3, the fiber include silkworm silk, Cotton Gossypii or Pilus Caprae seu Oviss.
Used as a total inventive concept, the present invention also provides a kind of above-mentioned titanio composite anode or by above-mentioned preparation side
Application of the titanio composite anode in electrolytic manganese, sewage disposal and chlorine industry obtained in method.
Compared with prior art, it is an advantage of the current invention that：1. the titania nanotube of densification and tin-antimony oxide structure
Into intermediate layer, can effectively suppress the passivation of oxygen and matrix, drastically increase the service life of electrode.2. titanium dioxide
Nanotube has larger specific surface area, and its tubular structure can strengthen the binding ability of substrate and tin-antimony oxide intermediate layer, energy
It is enough effectively to prevent modified coatings from coming off in the course of the work.3. between the cellular tin-antimony oxide layer for preparing and active surface layer
There is preferable binding ability, be prevented from active coating coming off in electrolytic process.4. manganese mixed with fiber, iridium, tantalum or ruthenium
The active surface layer that after saline solution coating prepared by Jing thermal decomposition methods has preferable electrocatalysis characteristic.If 5. active surface layer is two
Manganese oxide, active coating can will not introduce other impurity as the substrate of deposition manganese dioxide, and the titanio composite anode can
Using with electrolytic manganese；If active layer is IrO2、Ta2O5、RuO2One or more when, the titanio composite anode can be applicable to sewage
Process and chlorine industry, the efficiency of oxidation Decomposition Organic substance is higher in sewage disposal.6. the use of electrode prepared by the present invention
Life-span is long more than common combination electrode.
Description of the drawings
In order to be illustrated more clearly that the embodiment of the present invention or technical scheme of the prior art, below will be to embodiment or existing
The accompanying drawing to be used needed for having technology description is briefly described, it should be apparent that, drawings in the following description are the present invention
Some embodiments, for those of ordinary skill in the art, on the premise of not paying creative work, can be with basis
These accompanying drawings obtain other accompanying drawings.
Fig. 1 is the structural representation of titanio composite anode of the present invention.
Fig. 2 is the sectional view of the cellular tin-antimony oxide layer of titanio composite anode of the present invention.
Fig. 3 is the sectional view of the titania nanotube of titanio composite anode of the present invention.
Fig. 4 is titanio composite anode prepared by embodiment 1（B）With do not contain titania nanotube and cellular stannum antimony oxygen
The titanio composite anode of compound layer（A）Intensified electrolysis curve comparison figure.
Fig. 5 is titanio composite anode prepared by embodiment 2（B）It is combined with the titanio for not containing cellular tin-antimony oxide layer
Anode（A）Current efficiency curve comparison figure.
Illustrate：1- Titanium bases；2- titania nanotubes；3- tin-antimony oxide compacted zones；The cellular stannum antimony oxygen of 4-
Compound layer；5- active surface layers.
Specific embodiment
For the ease of understanding the present invention, more complete is made to the present invention below in conjunction with Figure of description and preferred embodiment
Face, meticulously describe, but protection scope of the present invention is not limited to embodiment in detail below.
Unless otherwise defined, the implication that all technical terms used hereinafter are generally understood that with those skilled in the art
It is identical.Technical term used herein is intended merely to describe the purpose of specific embodiment, is not intended to limit the present invention
Protection domain.
Unless otherwise specified, various raw materials, reagent, instrument and equipment used in the present invention etc. can pass through city
Field is commercially available or can be prepared by existing method.
Embodiment 1
A kind of long-life titanio composite anode of the present invention, as shown in figure 1, the titanio composite anode includes Titanium base 1
（It is metallic titanium plate in the present embodiment）, double fine and close protection intermediate layers, active surface layer 5；Wherein double fine and close protection intermediate layers are divided into
Two-layer, ground floor is titania nanotube 2, and the second layer is tin-antimony oxide compacted zone 3；Above-mentioned tin-antimony oxide compacted zone 3
It is upper to be covered with cellular tin-antimony oxide layer 4 again；Active surface layer 5 is MnO2Metal-oxide.Fig. 2 is that the titanio of the present invention is combined
The sectional view of the cellular tin-antimony oxide layer 4 of anode；Fig. 3 is the titania nanotube 2 of the titanio composite anode of the present invention
Sectional view.
The preparation method of the titanio composite anode of the present embodiment, comprises the following steps：
(1) thickness is cut into the specification of 2 × 2cm for the titanium plate of 1.2mm, then with sand papering, in the 5w% for boiling
Alkali cleaning oil removing 1h in NaOH solution, in the 10w% oxalic acid solutions of boiling 1h is etched, and then deionized water is rinsed well, is obtained
The titanium plate of clean surface.
(2) preparation in double fine and close protection intermediate layers：
The preparation of titania nanotube 2：Using surface treated titanium plate as anode, graphite electrode as negative electrode,
6h is electrolysed in the glycerin solution containing 3.5g/LNaF, the water content of electrolyte is 5g/L, and constant voltage is 40V, electrolysis temperature
Spend for 25 DEG C, pole span is 4cm；Then by electrode clean totally in 500 DEG C of roasting 1h.
The preparation of tin-antimony oxide compacted zone 3：9.61g citric acids and 12.41g ethylene glycol are mixed, is reacted at 55 DEG C
1h, is subsequently adding 5.25g SnCl4·5H2O and 0.342g SbCl3, 1h is reacted at 90 DEG C, prepare polymer precursor molten
Liquid；Polybenzazole precursor liquid solution is coated in through the titanium plate surface of anodized, the roasting 30min at 500 DEG C, this step
Suddenly it is repeated 10 times, last time roasting 1h.
(3) preparation of cellular tin-antimony oxide layer 4：Use respectively（Mass fraction is 10%）Sodium hydroxide and deionized water
Washing methyl methacrylate（MMA）Three times, take 13gMMA and 150g deionized waters and be added in the round-bottomed flask of 500ml and stir
Mix.It is subsequently adding 12gK2S2O87h is reacted after mix homogeneously under 50 ~ 90 DEG C and nitrogen atmosphere.By the milky white liquid mistake for obtaining
Filter, removes and be obtained after aggregate polymethyl methacrylate（PMMA）.Then the electrode for preparing is infiltrated in the liquid,
Again electrode being dried into 24h at 70 DEG C can obtain the gluey crystallization templates of PMMA on surface.
6g phenol and sodium hydroxide solution that 1g, mass fraction are 20% are mixed and stirred for, 10g formaldehyde is added, will be transparent
Solution stir 1h at 75 DEG C.After being cooled to room temperature, 2mol L are used-1Hydrochloric acid the pH of solution is adjusted to into 7, then solution is steamed
Evaporate, then dissolved with the ethanol of 10ml, sodium chloride crystal unnecessary in solution is filtered to remove, filtrate is that P-F gathers
Compound precursor solution, in case next step is used.
By the stannic chloride and antimony chloride of 2g（The muriatic mol ratio of stannum antimony is 10:1）Add ethanol solution and stir
30min, addition 1g phenol-formaldehyde polymers precursor liquid is stirred for 1h into the solution.Add 0.11g polypropylene glycols and epoxy again
The addition polymers of ethane（F127）, and stir acquisition target liquid.During the electrode for having PMMA is immersed dissolved with above-mentioned target liquid, after taking-up
Dry and dry 2h at 100 DEG C after unnecessary solution, this process is repeated 3 times, to guarantee space of the target liquid full of template.Then in Ar
In atmosphere, roasting 2h at 450 DEG C, then the roasting 3h at 800 DEG C again（Heating rate is 1 DEG C/min）, you can it is obtained cellular
Tin-antimony oxide layer 4.
(4) preparation of active surface layer 5：The manganese nitrate solution of 50w% is applied on the intermediate layer, the roasting at 500 DEG C
30min, this overshoot is repeated 10 times；Then the manganese nitrate solution containing silkworm silk is applied, the roasting 30min at 500 DEG C, this overshoot weight
Multiple 4 times, last time roasting 1h obtains long-life titanio composite anode of the present embodiment.
Application of the titanio composite anode of the present embodiment in electrolytic manganese：As a comparison, it is prepared under the same conditions not
Two kinds of electrodes have been carried out the reinforcing longevity by the titanio composite anode containing titania nanotube 2 and cellular tin-antimony oxide layer 4
Life test, has obtained the result as shown in Fig. 4, and A is represented and do not contained titania nanotube 2 and cellular tin-antimony oxide layer 4
Titanio composite anode, B represents the titanio composite anode of the present embodiment, by contrast it is found that there is titania nanotube 2
Greatly improved with the life-span of the titanio composite anode of cellular tin-antimony oxide layer 4.
Embodiment 2
A kind of long-life titanio composite anode of the present invention, as shown in figure 1, the titanio composite anode includes Titanium base 1
（It is metallic titanium plate in the present embodiment）, double fine and close protection intermediate layers, active surface layer 5；Wherein double fine and close protection intermediate layers are divided into
Two-layer, ground floor is titania nanotube 2, and the second layer is tin-antimony oxide compacted zone 3；Above-mentioned tin-antimony oxide compacted zone 3
It is upper to be covered with cellular tin-antimony oxide layer 4 again；Active surface layer 5 is MnO2Metal-oxide.
The preparation method of the titanio composite anode of the present embodiment, comprises the following steps：
(1) thickness is cut into the specification of 2 × 2cm for the titanium plate of 1.2mm, then with sand papering, in the 5w% for boiling
In NaOH solution alkali cleaning oil removing 1h and boiling 10w% oxalic acid solutions in etch 1h, then deionized water is rinsed well, is obtained
To the titanium plate of clean surface.
(2) preparation in double fine and close protection intermediate layers：
The preparation of titania nanotube 2：Using surface treated titanium plate as anode, graphite electrode as negative electrode,
It is electrolysed 4h in the glycerin solution containing 8g/LNaF, the water content of electrolyte is 4g/L, constant voltage is 50V, electrolysis temperature
For 25 DEG C, pole span is 4cm.Then by electrode clean totally in 500 DEG C of roasting 1h.
The preparation of tin-antimony oxide compacted zone 3：9.61g citric acids and 12.41g ethylene glycol are mixed, is reacted at 65 DEG C
1h, is subsequently adding 8.75g SnCl4·5H2O and 0.57g SbCl3, 1h is reacted at 90 DEG C, prepare polymer precursor
Solution；Polybenzazole precursor liquid solution is coated in through the titanium plate surface of anodized, the roasting 30min at 500 DEG C, this
Step is repeated 10 times, last time roasting 1h.
（3）The preparation of cellular tin-antimony oxide layer 4：Use respectively（Mass fraction is 10%）Sodium hydroxide and deionized water
Washing methyl methacrylate（MMA）Three times, take 15gMMA and 180g deionized waters and be added in the round-bottomed flask of 500ml and stir
Mix.It is subsequently adding 15gK2S2O87h is reacted after mix homogeneously under 90 DEG C and nitrogen atmosphere.The milky white liquid for obtaining is filtered,
Remove and be obtained after aggregate polymethyl methacrylate（PMMA）.Then the electrode for preparing is infiltrated in the liquid, then
Electrode is dried into 24h at 70 DEG C can obtain the gluey crystallization templates of PMMA on surface.
8g phenol and sodium hydroxide solution that 1.5g mass fractions are 20% are mixed and stirred for, 14g formaldehyde is added, will be saturating
Bright solution stirs 1h at 75 DEG C.After being cooled to room temperature, 2mol L are used-1HCl the pH of solution is adjusted to into 7.Then by solution
Distill, then the ethanol of 10ml is dissolved.Sodium chloride crystal unnecessary in solution is filtered to remove, filtrate is that P-F gathers
Compound precursor solution, in case next step is used.
By the stannic chloride of 2g and antimony chloride mixture（The muriatic mol ratio of stannum antimony is 10:1）Add ethanol solution and stir
Mix 30min.Addition 1.4g phenol-formaldehyde polymers precursor liquid is stirred for 1h into the solution.Add 0.15g F127 again and stir
Mix acquisition target liquid.The electrode for having PMMA is immersed in above-mentioned target liquid, is dried after taking-up after unnecessary solution in 100 DEG C of bakings
2h, this process is repeated 3 times, to guarantee space of the target liquid full of template.Then in an ar atmosphere, roasting 2h at 450 DEG C, then
The roasting 3h at 800 DEG C again（Heating rate is 1 DEG C/min）, you can cellular tin-antimony oxide layer 4 is obtained.
(4) preparation of active surface layer 5：The manganese nitrate solution of 50w% is applied on the intermediate layer, the roasting at 500 DEG C
30min, this overshoot is repeated 10 times；Then the manganese nitrate solution containing silkworm silk is applied, the roasting 30min at 500 DEG C, this overshoot weight
Multiple 8 times, last time roasting 1h obtains long-life titanio composite anode of the present embodiment.
Application of the titanio composite anode of the present embodiment in electrolytic manganese：As a comparison, it is prepared under the same conditions not
Two kinds of electrodes have been carried out reinforcing life test by the titanio composite anode containing cellular tin-antimony oxide layer 4, have been obtained such as figure
5 shown result, A represents the titanio composite anode for not containing cellular tin-antimony oxide layer 4, and B represents the titanio of the present embodiment
Composite anode, by contrast it is found that the life-span for having the titanio composite anode of cellular tin-antimony oxide layer 4 has obtained necessarily
Raising.
Embodiment 3
A kind of long-life titanio composite anode of the present invention, as shown in figure 1, the titanio composite anode includes Titanium base 1
（It is metallic titanium plate in the present embodiment）, double fine and close protection intermediate layers, active surface layer 5；Wherein double fine and close protection intermediate layers are divided into
Two-layer, ground floor is titania nanotube 2, and the second layer is tin-antimony oxide compacted zone 3；Above-mentioned tin-antimony oxide compacted zone 3
It is upper to be covered with cellular tin-antimony oxide layer 4 again；Active surface layer 5 is MnO2Metal-oxide.
The preparation method of the titanio composite anode of the present embodiment, comprises the following steps：
(1) thickness is cut into the specification of 2 × 2cm for the titanium plate of 1.2mm, then with sand papering, in the 5w% for boiling
In NaOH solution alkali cleaning oil removing 1h and boiling 10w% oxalic acid solutions in etch 1h, then deionized water is rinsed well, is obtained
To the titanium plate of clean surface.
(2) preparation in double fine and close protection intermediate layers
The preparation of titania nanotube 2：Using surface treated titanium plate as anode, graphite electrode as negative electrode,
It is electrolysed 4h in the glycerin solution containing 6g/LNaF, the water content of electrolyte is 8g/L, constant voltage is 35V, electrolysis temperature
For 25 DEG C, pole span is 4cm.Then by electrode clean totally in 500 DEG C of roasting 1h.
The preparation of tin-antimony oxide compacted zone 3：9.61g citric acids and 12.41g ethylene glycol are mixed, is reacted at 60 DEG C
1h, is subsequently adding 4.375g SnCl4·5H2O and 0.57g SbCl3, 1h is reacted at 90 DEG C, prepare polymer precursor
Solution；Polybenzazole precursor liquid solution is coated in through the titanium plate surface of anodized, the roasting 30min at 500 DEG C, this
Step is repeated 10 times, last time roasting 1h.
（3）The preparation of cellular tin-antimony oxide layer 4：Use respectively（Mass fraction is 10%）Sodium hydroxide and deionized water
Washing methyl methacrylate（MMA）Three times, take 9gMMA and 120ml deionized waters and be added in the round-bottomed flask of 500ml and stir
Mix.It is subsequently adding 8gK2S2O87h is reacted after mix homogeneously under 50 ~ 90 DEG C and nitrogen atmosphere.By the milky white liquid mistake for obtaining
Filter, removes and be obtained after aggregate polymethyl methacrylate（PMMA）.Then the electrode for preparing is infiltrated in the liquid,
Again electrode being dried into 24h at 70 DEG C can obtain the gluey crystallization templates of PMMA on surface.
4g phenol and sodium hydroxide solution that 0.7g, mass fraction are 20% are mixed and stirred for, 7g formaldehyde is added, will be saturating
Bright solution stirs 1h at 75 DEG C.After being cooled to room temperature, 2mol L are used-1Hydrochloric acid the pH of solution is adjusted to into 6.Then by solution
Distillation, then dissolved with the ethanol of 10ml.Sodium chloride crystal unnecessary in solution is filtered to remove, filtrate is P-F
Polybenzazole precursor liquid solution, in case next step is used.
By the stannic chloride and antimony chloride of 2g（The muriatic mol ratio of stannum antimony is 12.5:1）Add ethanol solution and stir
30min, addition 0.8g phenol-formaldehyde polymers precursor liquid is stirred for 1h into the solution.Add 0.08gF127 again and stir,
Obtain target liquid.The electrode for having PMMA is immersed into above-mentioned target liquid, to be dried after taking-up and dry 2h at 100 DEG C after unnecessary solution, this
Process is repeated 3 times, to guarantee space of the target liquid full of template.Then in an ar atmosphere, 450 DEG C of roasting 2h, then again 800
Roasting 3h at DEG C（Heating rate is 1 DEG C/min）.Can be prepared by cellular tin-antimony oxide layer 4.
(4) preparation of active surface layer 5：The manganese nitrate solution of 50w% is applied on the intermediate layer, the roasting at 500 DEG C
30min, this overshoot is repeated 10 times；Then the manganese nitrate solution containing silkworm silk is applied, the roasting 30min at 500 DEG C, this process repeats
6 times, last time roasting 1h obtains long-life titanio composite anode of the present embodiment.
Application of the titanio composite anode of the present embodiment in electrolytic manganese：As a comparison, it is prepared under the same conditions not
The titanio composite anode of the manganese nitrate solution containing silkworm silk is applied, two kinds of electrodes have been carried out with electrolysis test, bath composition is：
MnSO4=17g/L、(NH4)2SO4=110g/L、SeO2=0.04g/L.The result as shown in table 1 is obtained, by experimental result pair
Than it is found that the titanio composite anode containing silkworm silk current efficiency than do not contain silkworm silk titanio composite anode current efficiency
It is high.
Table 1
Claims (8)
1. a kind of preparation method of titanio composite anode, the titanio composite anode includes Titanium base, double fine and close protection intermediate layers, work
Property surface layer；Double fine and close protection intermediate layers are divided into two-layer, and ground floor is titania nanotube, and the second layer is the oxidation of stannum antimony
Thing compacted zone；Cellular tin-antimony oxide layer is covered with the tin-antimony oxide compacted zone again；Characterized in that, the titanio is multiple
The preparation method of Heyang pole is comprised the following steps：
（1）By Titanium base polishing, alkali cleaning or pickling, the Titanium base of clean surface is obtained；
（2）The preparation in double fine and close protection intermediate layers：
The preparation of titania nanotube：Using through the Titanium base of above-mentioned process, used as anode, graphite electrode is containing as negative electrode
Have in the alcohols electrolyte of NaF and be electrolysed, then Titanium base is carried out into roasting, obtain the electrode containing titania nanotube；
The preparation of tin-antimony oxide compacted zone：Citric acid and ethylene glycol are mixed, reacting by heating is subsequently adding pink salt and antimonic salt,
Reacting by heating, prepares polybenzazole precursor liquid solution, and above-mentioned polybenzazole precursor liquid solution is coated in into above-mentioned electrode surface, roasting
Burn, this process repeats 10 ~ 15 times, obtains the electrode containing the tin-antimony oxide compacted zone；
（3）Cellular tin-antimony oxide layer：Above-mentioned electrode is infiltrated in polymethyl methacrylate liquid, drying obtains table
Face is covered with the electrode of the gluey crystallization template of polymethyl methacrylate；
In the ethanol solution containing pink salt and antimonic salt, after stirring, addition is poly- for addition phenol-formaldehyde polymer precursor solution
Propylene Glycol and the addition polymers of oxirane, stir, and obtain target liquid, above-mentioned electrode are immersed in above-mentioned target liquid, drying
Roasting afterwards, you can the electrode containing cellular tin-antimony oxide layer is obtained；
（4）The preparation of active surface layer：One or more in manganese, iridium, tantalum or ruthenium saline solution are coated in into the table of above-mentioned electrode
Face, roasting, this process repeats 10 ~ 15 times；One or more in the manganese containing fiber, iridium, tantalum or ruthenium saline solution are then coated with,
Roasting, this process repeats 4 ~ 8 times, that is, obtain the titanio composite anode；
The Titanium base is metallic titanium plate, titanium alloy or titanium thin slice；The active surface layer is MnO2、IrO2、Ta2O5、RuO2In
One or more mixed-metal oxides.
2. preparation method as claimed in claim 1, it is characterised in that the electrode is infiltrated in polymethyl methacrylate liquid
The temperature of body post-drying is 70 DEG C, and the time is 24h；It is 90 ~ 110 by the temperature that the electrode immerses the target liquid post-drying
DEG C, the time is 0.5 ~ 3h, and this process repeats 3 ~ 5 times；
The step（2）Middle to add after the citric acid and ethylene glycol, the temperature of reacting by heating is 55 ~ 65 DEG C, adds the stannum
After salt and antimonic salt, the temperature of reacting by heating is 85 ~ 95 DEG C；
The step（2）、（4）In roasting temperature be 450 DEG C ~ 550 DEG C, the time be 30min ~ 180min；
The step（3）The process conditions of middle roasting are：In an ar atmosphere, 1 ~ 4h of roasting at 400 ~ 480 DEG C, then 780 ~
2 ~ 5h of roasting at 850 DEG C, heating rate is controlled in 1 ~ 2 DEG C/min.
3. preparation method as claimed in claim 1, it is characterised in that the time of the electrolysis is 1h ~ 6h, electrolyte during electrolysis
Water content control between 1g/L ~ 10g/L, voltage control between 15V ~ 75V.
4. preparation method as claimed in claim 1, it is characterised in that the step（2）With step（3）In pink salt be
SnCl45H2O, antimonic salt is SbCl3；Wherein step（2）Middle citric acid, ethylene glycol, pink salt, antimonic salt mol ratio be 1: 4: 0 ~
0.5∶0~0.1。
5. the preparation method as any one of claim 1 ~ 4, it is characterised in that the polymethyl methacrylate liquid
Preparation comprise the following steps：Respectively methyl methacrylate is washed into three times with sodium hydroxide and deionized water, then by with
Lower weight portion and parts by volume addition raw material：7 ~ 15 parts by weight of methylmethacrylate；90 ~ 200 parts by volume deionized waters；7 ~ 15 weights
Amount part K2S2O8；5 ~ 9h is reacted under 50 ~ 90 DEG C and nitrogen atmosphere after mix homogeneously, is filtered, removed and be obtained after aggregate poly- first
Base acrylic acid methyl ester. liquid；
The unit ratio corresponding relation of the weight portion and parts by volume is g/ml.
6. the preparation method as any one of claim 1 ~ 4, it is characterised in that the phenol-formaldehyde polymer forerunner
The preparation of liquid solution is comprised the following steps：By the phenol of 3 ~ 9 weight portions and hydroxide that 0.2 ~ 3 weight portion, mass fraction are 20%
Sodium solution is mixed and stirred for, and is subsequently adding 8 ~ 14 parts by weight of formaldehyde, and at 60 ~ 80 DEG C 1h is stirred, after being cooled to room temperature, with 1 ~
The pH of solution is adjusted to 5 ~ 8 by the hydrochloric acid of 4mol L-1, then distills solution, then is dissolved with ethanol, will be unnecessary in solution
Sodium chloride crystal be filtered to remove, the i.e. described phenol-formaldehyde polymer precursor solution of filtrate.
7. the preparation method as any one of claim 1 ~ 4, it is characterised in that the manganese, iridium, tantalum or ruthenium salt are respectively
Mn (NO3) 2, IrCl3, TaCl5, RuCl3, the fiber includes silkworm silk, Cotton Gossypii or Pilus Caprae seu Oviss.
8. one kind as obtained in claim 1 ~ 7 any one preparation method titanio composite anode electrolytic manganese, sewage disposal and
Application in chlorine industry.
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