CN104593818A - 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, particularly relate to a kind of composite anode and its preparation method and application.
Background technology
The advantages such as titanium based composite anode is with titanium or titanium alloy for matrix, the electrode that the metal oxide of coating Sb, Ir, Sn, Mn isoreactivity element is formed, and has catalytic activity high, delays matrix passivation, and the selectivity of reaction is better.Traditional electrode, as graphite anode intensity is not high, lead silver alloy anode has plumbous dissolving and enters the shortcomings such as electrolytic solution.Titanium based composite anode can according to the different purposes of electrode and requirement, designs targetedly, reduce the generation of side reaction, improve productive rate and the current efficiency of target product with this coating of electrode and structure.This titanium based composite anode is widely used in manganese electrolytic industry, chlorine industry, the fields such as sewage disposal.
The preparation method of titanium based composite anode mainly contains the methods such as thermal decomposition method, sol-gel method, magnetron sputtering method, electrochemical deposition method, the structure and activity that different preparation methods obtains coating is different, the obtained coating densification of electrochemical deposition method thus its life-span longer, the obtained coating catalytic activity of thermal decomposition method is higher.But also the ratio of component can be regulated to regulate activity and the structure of coating.Therefore experimentally can determine that good coating proportion of composing, maturing temperature and a series of electrolytic condition prepare active higher titanium based composite anode.
Although the preparation method of titanium based composite anode is varied, technique is simple, and the catalytic activity of coating is high, and selectivity is good, has the shortcoming that fatal: work-ing life is shorter.Numerous investigator is in order to address this problem in recent years, proposes a lot of scheme, does a lot of experiment.The major cause of electrode inactivation is that Titanium base is oxidized, Titanium base Surface Creation one deck passive film, or active substance comes off or dissolved.Shi Yanhua etc. use the oxide compound of Sn, Sb as middle layer, the bonding force of enhanced activity layer and matrix, and delay passivation (the Effect of SbO of oxygen to matrix
x+ SnO
2intermediate Layer on the Properties of Ti-based MnO
2anode [J] .Acta Phys. Chim. Sin., 2007,23 (10): 1553-1559.), but also find middle layer and the active coating densification all not of preparation, delay oxygen still not ideal enough to the action effect of matrix passivation.The content increasing middle layer can reduce oxygen evolution potential, and this is disadvantageous to the application of titanium based composite anode, and such as, in the process of disposing of sewage, oxygen evolution potential is low is unfavorable for that organism is oxidized anodically and is beneficial to precipitated oxygen, thus reduces current efficiency.
Summary of the invention
Technical problem to be solved by this invention is, overcomes the deficiency and defect mentioned in above background technology, provides a kind of long service life, titanium based composite anode that electro catalytic activity is good and its preparation method and application.
For solving the problems of the technologies described above, the technical scheme that the present invention proposes is a kind of titanium based composite anode, and this titanium based composite anode comprises Titanium base, two densification protection middle layer, active surface layer; Described two fine and close protection middle layer is divided into two-layer, and the first layer is titania nanotube, and the second layer is tin-antimony oxide tight zone; Described tin-antimony oxide tight zone is covered with again cellular tin-antimony oxide layer.
Above-mentioned titanium based composite anode, preferably, described Titanium base is metallic titanium plate, titanium alloy or titanium thin slice; Described active surface layer is MnO
2, IrO
2, Ta
2o
5, RuO
2in one or more mixed metal oxide.
As a total inventive concept, present invention also offers a kind of preparation method of above-mentioned titanium based composite anode, comprise the following steps:
(1) by Titanium base polishing, alkali cleaning or pickling, the Titanium base of clean surface is obtained;
(2) preparation in two densification protection middle layer:
The preparation of titania nanotube: using the Titanium base through above-mentioned process as anode, Graphite Electrodes, as negative electrode, carries out electrolysis, then Titanium base is carried out roasting in the alcohols electrolytic solution containing NaF, obtains the electrode containing titania nanotube;
The preparation of tin-antimony oxide tight zone: by citric acid and ethylene glycol mixing, reacting by heating, then pink salt and antimonic salt is added, reacting by heating, prepare polybenzazole precursor liquid solution, above-mentioned polybenzazole precursor liquid solution is coated in above-mentioned electrode surface, roasting, this process repeats 10 ~ 15 times, must containing the electrode of described tin-antimony oxide tight zone;
(3) cellular tin-antimony oxide layer: infiltrated in polymethylmethacrylate liquid by above-mentioned electrode, dries, and obtains the electrode that surface is covered with the gluey crystallization template of polymethylmethacrylate;
Add phenol-formaldehyde polymer precursor solution in the ethanolic soln containing pink salt and antimonic salt, after stirring, add the addition polymer of polypropylene glycol and oxyethane, stir, obtain target liquid, immersed by above-mentioned electrode in above-mentioned target liquid, roasting after drying, can obtain the electrode containing cellular tin-antimony oxide layer;
(4) preparation of active surface layer: the surface one or more in manganese, iridium, tantalum or ruthenium salts solution being coated in above-mentioned electrode, roasting, this process repeats 10 ~ 15 times; Then apply one or more in manganese, iridium, tantalum or the ruthenium salts solution containing fiber, roasting, this process repeats 4 ~ 8 times, namely obtains described titanium based composite anode.
The present invention by anode oxidation method, prepares layer of titanium dioxide nanotube between matrix and tin-antimony oxide tight zone, by improving the binding ability in middle layer and substrate thus improve work-ing life of electrode, can also ensure that electrode has good catalytic activity.The present invention also passes through template; prepare the cellular tin-antimony oxide of one deck in two densification protection interlayer surfaces, improve the specific surface area in middle layer, to strengthen the binding ability in middle layer and active surface layer; inhibit coming off of surfactivity layer, extend the life-span of electrode.In manganese, iridium, tantalum or ruthenium salts solution, add appropriate Mierocrystalline cellulose, increased the specific surface area of active coating by pore-creating, for the catalyzed reaction occurring in surface provides more reactive behavior point, thus improve the catalytic capability of electrode.
In above-mentioned preparation method, preferably, infiltrating described electrode in the temperature of polymethylmethacrylate liquid post-drying is 70 DEG C, and the time is 24h; The temperature described electrode being immersed described target liquid post-drying is 90 ~ 110 DEG C, and the time is 0.5 ~ 3h, and this process repeats 3 ~ 5 times; After adding described citric acid and ethylene glycol in described step (2), the temperature of reacting by heating is 55 ~ 65 DEG C, and after adding described pink salt and antimonic salt, the temperature of reacting by heating is 85 ~ 95 DEG C; The temperature of the roasting in described step (2), (4) is 450 DEG C ~ 550 DEG C, and the time is 30min ~ 180min;
In described step (3), the processing condition of roasting are: in an ar atmosphere, roasting 1 ~ 4h at 400 ~ 480 DEG C, then roasting 2 ~ 5h at 780 ~ 850 DEG C, temperature rise rate controls at 1 ~ 2 DEG C/min.
In above-mentioned preparation method, preferably, the time of described electrolysis is 1h ~ 6h, and during electrolysis, the water content control of electrolytic solution is between 1g/L ~ 10g/L, and voltage control is between 15V ~ 75V.
In above-mentioned preparation method, preferably, described step (2) is SnCl with the pink salt in step (3)
45H
2o, antimonic salt is SbCl
3; Wherein in step (2), the mol ratio of citric acid, ethylene glycol, pink salt, antimonic salt is 1: 4: 0 ~ 0.5: 0 ~ 0.1.In above-mentioned preparation method, preferably, the preparation of described polymethylmethacrylate liquid comprises the following steps: with sodium hydroxide and deionized water, methyl methacrylate is washed three times respectively, then adds raw material by following weight part and parts by volume: 7 ~ 15 parts by weight of methylmethacrylate; 90 ~ 200 parts by volume deionized waters; 7 ~ 15 weight part K
2s
2o
8; Under 50 ~ 90 DEG C and nitrogen atmosphere, react 5 ~ 9h after mixing, filter, after removing aggregate, namely obtain polymethylmethacrylate (PMMA) liquid;
The unit ratio corresponding relation of described weight part and parts by volume is g/ml.
In above-mentioned preparation method, preferably, the preparation of described phenol-formaldehyde polymer precursor solution comprises the following steps: the sodium hydroxide solution being 20% by the phenol of 3 ~ 9 weight parts and 0.2 ~ 3 weight part, massfraction mixes and stirs, 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 the pH of solution is adjusted to 5 ~ 8, then solution is distilled, then to be dissolved with a certain amount of ethanol, sodium chloride crystal unnecessary in solution is crossed and filters, the phenol-formaldehyde polymer precursor solution that filtrate is namely described.
In above-mentioned preparation method, preferably, described manganese, iridium, tantalum or ruthenium salt are respectively Mn (NO
3)
2, IrCl
3, TaCl
5, RuCl
3, described fiber comprises silk, cotton or wool.
As a total inventive concept, the application of titanium based composite anode in electrolytic manganese, sewage disposal and chlorine industry that the present invention also provides a kind of above-mentioned titanium based composite anode or obtained by above-mentioned preparation method.
Compared with prior art, the invention has the advantages that: 1. the titania nanotube of densification and tin-antimony oxide form middle layer, effectively can suppress the passivation of oxygen and matrix, drastically increase the work-ing life of electrode.2. titania nanotube has larger specific surface area, and its tubular structure can strengthen the binding ability in substrate and tin-antimony oxide middle layer, can effectively prevent finish coat from coming off in the course of the work.3. there is good binding ability between the cellular tin-antimony oxide layer prepared and active surface layer, activated coating coming off in electrolytic process can be prevented.4. the active surface layer prepared through thermal decomposition method after being mixed with the coating of the manganese of fiber, iridium, tantalum or ruthenium salts solution has good electrocatalysis characteristic.If 5. active surface layer is Manganse Dioxide, activated coating as the substrate of deposited silicon dioxide manganese, can not introduce other impurity, and this titanium based composite anode can be applied and electrolytic manganese; If active coating is IrO
2, Ta
2o
5, RuO
2one or more time, this titanium based composite anode can be applicable to sewage disposal and chlorine industry, and in sewage disposal, the organic efficiency of oxygenolysis is higher.6. the present invention is long more than common combined electrode for work-ing life of electrode of preparing.
Accompanying drawing explanation
In order to be illustrated more clearly in the embodiment of the present invention or technical scheme of the prior art, be briefly described to the accompanying drawing used required in embodiment or description of the prior art below, apparently, accompanying drawing in the following describes is some embodiments of the present invention, for those of ordinary skill in the art, under the prerequisite not paying creative work, other accompanying drawing can also be obtained according to these accompanying drawings.
Fig. 1 is the structural representation of titanium based composite anode of the present invention.
Fig. 2 is the sectional view of the cellular tin-antimony oxide layer of titanium based composite anode of the present invention.
Fig. 3 is the sectional view of the titania nanotube of titanium based composite anode of the present invention.
Fig. 4 is the intensified electrolysis curve comparison figure of the titanium based composite anode (B) prepared of embodiment 1 and the titanium based composite anode (A) that do not contain titania nanotube and cellular tin-antimony oxide layer.
Fig. 5 is the current efficiency curve comparison figure of the titanium based composite anode (B) of embodiment 2 preparation and the titanium based composite anode (A) not containing cellular tin-antimony oxide layer.
Illustrate: 1-Titanium base; 2-titania nanotube; 3-tin-antimony oxide tight zone; The cellular tin-antimony oxide layer of 4-; 5-active surface layer.
Embodiment
For the ease of understanding the present invention, hereafter will do to describe more comprehensively, meticulously to the present invention in conjunction with Figure of description and preferred embodiment, but protection scope of the present invention is not limited to following specific embodiment.
Unless otherwise defined, hereinafter used all technical terms are identical with the implication that those skilled in the art understand usually.The object of technical term used herein just in order to describe specific embodiment is not be intended to limit the scope of the invention.
Unless otherwise specified, the various starting material, reagent, instrument and equipment etc. used in the present invention are all bought by market and are obtained or prepare by existing method.
embodiment 1
A kind of long-life titanium based composite anode of the present invention, as shown in Figure 1, it is metallic titanium plate that this titanium based composite anode comprises in Titanium base 1(the present embodiment), two densification protection middle layer, active surface layer 5; Wherein two densification protection middle layer is divided into two-layer, and the first layer is titania nanotube 2, and the second layer is tin-antimony oxide tight zone 3; Above-mentioned tin-antimony oxide tight zone 3 is covered with again cellular tin-antimony oxide layer 4; Active surface layer 5 is MnO
2metal oxide.Fig. 2 is the sectional view of the cellular tin-antimony oxide layer 4 of titanium based composite anode of the present invention; Fig. 3 is the sectional view of the titania nanotube 2 of titanium based composite anode of the present invention.
The preparation method of the titanium based composite anode of the present embodiment, comprises the following steps:
(1) by thickness be the specification that the titanium plate of 1.2mm cuts into 2 × 2cm, then use sand papering, alkali cleaning oil removing 1h in the 5w%NaOH solution boiled, in the 10w% oxalic acid solution of boiling, etch 1h, then clean with deionized water rinsing, obtain the titanium plate of clean surface.
(2) preparation in two densification protection middle layer:
The preparation of titania nanotube 2: using surface treated titanium plate as anode, Graphite Electrodes as negative electrode, electrolysis 6h in containing the glycerin solution of 3.5g/LNaF, the water content of electrolytic solution is 5g/L, constant voltage is 40V, and electrolysis temperature is 25 DEG C, and pole span is 4cm; Then by electrode clean totally at 500 DEG C of roasting 1h.
The preparation of tin-antimony oxide tight zone 3: by 9.61g citric acid and the mixing of 12.41g ethylene glycol, react 1h at 55 DEG C, then add 5.25g SnCl
45H
2o and 0.342g SbCl
3, at 90 DEG C of reaction 1h, prepare polybenzazole precursor liquid solution; Polybenzazole precursor liquid solution is coated in the titanium plate surface through anodic oxidation treatment, roasting 30min at 500 DEG C, this step repeats 10 times, last roasting 1h.
(3) preparation of cellular tin-antimony oxide layer 4: use (massfraction is 10%) sodium hydroxide and deionized water wash methyl methacrylate (MMA) three times respectively, gets 13gMMA and 150g deionized water and to join in the round-bottomed flask of 500ml and to stir.Then 12gK is added
2s
2o
8under 50 ~ 90 DEG C and nitrogen atmosphere, 7h is reacted after mixing.The milky white liquid obtained is filtered, after removing aggregate, namely obtains polymethylmethacrylate (PMMA).Then the electrode for preparing is infiltrated in this liquid, then electrode is dried at 70 DEG C 24h and can obtain the gluey crystallization template of PMMA on surface.
The sodium hydroxide solution being 20% by 6g phenol and 1g, massfraction mixes and stirs, and adds 10g formaldehyde, transparent solution is stirred 1h at 75 DEG C.After being cooled to room temperature, use 2mol L
-1hydrochloric acid the pH of solution is adjusted to 7, then solution is distilled, then to be dissolved with the ethanol of 10ml, sodium chloride crystal unnecessary in solution is crossed and filters, filtrate and phenol-formaldehyde polymer precursor solution, in order to next step use.
The tin chloride of 2g and antimony chloride (the muriatic mol ratio of tin antimony is 10:1) are added ethanolic soln and stir 30min, adds 1g phenol-formaldehyde polymer precursor liquid and enter this solution stirred for additional 1h.Add the addition polymer (F127) of 0.11g polypropylene glycol and oxyethane again, and stir acquisition target liquid.Immerse there being the electrode of PMMA and be dissolved with in above-mentioned target liquid, dry 2h at 100 DEG C after drying unnecessary solution after taking-up, this process repeats 3 times, to guarantee that target liquid is full of the space of template.Then in an ar atmosphere, roasting 2h at 450 DEG C, and then roasting 3h(temperature rise rate is 1 DEG C/min at 800 DEG C), cellular tin-antimony oxide layer 4 can be obtained.
(4) preparation of active surface layer 5: by the coating of the manganese nitrate solution of 50w% on the intermediate layer, roasting 30min at 500 DEG C, this overshoot repeats 10 times; Then the manganese nitrate solution of coating containing silk, roasting 30min at 500 DEG C, this overshoot repeats 4 times, last roasting 1h, namely obtains long-life titanium based composite anode of the present embodiment.
The application of titanium based composite anode in electrolytic manganese of the present embodiment: as a comparison, prepare the titanium based composite anode not containing titania nanotube 2 and cellular tin-antimony oxide layer 4 under the same conditions, reinforcing life test has been carried out to two kinds of electrodes, obtain result as shown in Fig. 4, A represents the titanium based composite anode not containing titania nanotube 2 and cellular tin-antimony oxide layer 4, B represents the titanium based composite anode of the present embodiment, can be found by contrast, have the life-span of the titanium based composite anode of titania nanotube 2 and cellular tin-antimony oxide layer 4 to obtain greatly to improve.
embodiment 2
A kind of long-life titanium based composite anode of the present invention, as shown in Figure 1, it is metallic titanium plate that this titanium based composite anode comprises in Titanium base 1(the present embodiment), two densification protection middle layer, active surface layer 5; Wherein two densification protection middle layer is divided into two-layer, and the first layer is titania nanotube 2, and the second layer is tin-antimony oxide tight zone 3; Above-mentioned tin-antimony oxide tight zone 3 is covered with again cellular tin-antimony oxide layer 4; Active surface layer 5 is MnO
2metal oxide.
The preparation method of the titanium based composite anode of the present embodiment, comprises the following steps:
(1) by thickness be the specification that the titanium plate of 1.2mm cuts into 2 × 2cm, then sand papering is used, alkali cleaning oil removing 1h and etch 1h in the 10w% oxalic acid solution of boiling in the 5w%NaOH solution boiled, then clean with deionized water rinsing, obtain the titanium plate of clean surface.
(2) preparation in two densification protection middle layer:
The preparation of titania nanotube 2: using surface treated titanium plate as anode, Graphite Electrodes as negative electrode, electrolysis 4h in containing the glycerin solution of 8g/LNaF, the water content of electrolytic solution is 4g/L, constant voltage is 50V, and electrolysis temperature is 25 DEG C, and pole span is 4cm.Then by electrode clean totally at 500 DEG C of roasting 1h.
The preparation of tin-antimony oxide tight zone 3: by 9.61g citric acid and the mixing of 12.41g ethylene glycol, react 1h at 65 DEG C, then add 8.75g SnCl
45H
2o and 0.57g SbCl
3, at 90 DEG C, react 1h, prepare polybenzazole precursor liquid solution; Polybenzazole precursor liquid solution is coated in the titanium plate surface through anodic oxidation treatment, roasting 30min at 500 DEG C, this step repeats 10 times, last roasting 1h.
(3) preparation of cellular tin-antimony oxide layer 4: use (massfraction is 10%) sodium hydroxide and deionized water wash methyl methacrylate (MMA) three times respectively, gets 15gMMA and 180g deionized water and to join in the round-bottomed flask of 500ml and to stir.Then 15gK is added
2s
2o
8under 90 DEG C and nitrogen atmosphere, 7h is reacted after mixing.The milky white liquid obtained is filtered, after removing aggregate, namely obtains polymethylmethacrylate (PMMA).Then the electrode for preparing is infiltrated in this liquid, then electrode is dried at 70 DEG C 24h and can obtain the gluey crystallization template of PMMA on surface.
The sodium hydroxide solution being 20% by 8g phenol and 1.5g massfraction mixes and stirs, and adds 14g formaldehyde, and transparent solution is stirred 1h at 75 DEG C.After being cooled to room temperature, use 2mol L
-1hCl the pH of solution is adjusted to 7.Then solution is distilled, then the ethanol of 10ml is dissolved.Sodium chloride crystal unnecessary in solution is crossed and filters, filtrate and phenol-formaldehyde polymer precursor solution, use in order to next step.
The tin chloride of 2g and antimony chloride mixture (the muriatic mol ratio of tin antimony is 10:1) are added ethanolic soln and stir 30min.Add 1.4g phenol-formaldehyde polymer precursor liquid and enter this solution stirred for additional 1h.Add 0.15g F127 again and stir and obtain target liquid.To the electrode of PMMA be had to immerse in above-mentioned target liquid, dry 2h at 100 DEG C after drying unnecessary solution after taking-up, this process repeats 3 times, to guarantee that target liquid is full of the space of template.Then in an ar atmosphere, roasting 2h at 450 DEG C, and then roasting 3h(temperature rise rate is 1 DEG C/min at 800 DEG C), cellular tin-antimony oxide layer 4 can be obtained.
(4) preparation of active surface layer 5: by the coating of the manganese nitrate solution of 50w% on the intermediate layer, roasting 30min at 500 DEG C, this overshoot repeats 10 times; Then the manganese nitrate solution of coating containing silk, roasting 30min at 500 DEG C, this overshoot repeats 8 times, last roasting 1h, namely obtains long-life titanium based composite anode of the present embodiment.
The application of titanium based composite anode in electrolytic manganese of the present embodiment: as a comparison, prepare the titanium based composite anode not containing cellular tin-antimony oxide layer 4 under the same conditions, reinforcing life test has been carried out to two kinds of electrodes, obtain result as shown in Fig. 5, A represents the titanium based composite anode not containing cellular tin-antimony oxide layer 4, B represents the titanium based composite anode of the present embodiment, can find have the life-span of the titanium based composite anode of cellular tin-antimony oxide layer 4 to obtain certain raising by contrast.
embodiment 3
A kind of long-life titanium based composite anode of the present invention, as shown in Figure 1, it is metallic titanium plate that this titanium based composite anode comprises in Titanium base 1(the present embodiment), two densification protection middle layer, active surface layer 5; Wherein two densification protection middle layer is divided into two-layer, and the first layer is titania nanotube 2, and the second layer is tin-antimony oxide tight zone 3; Above-mentioned tin-antimony oxide tight zone 3 is covered with again cellular tin-antimony oxide layer 4; Active surface layer 5 is MnO
2metal oxide.
The preparation method of the titanium based composite anode of the present embodiment, comprises the following steps:
(1) by thickness be the specification that the titanium plate of 1.2mm cuts into 2 × 2cm, then sand papering is used, alkali cleaning oil removing 1h and etch 1h in the 10w% oxalic acid solution of boiling in the 5w%NaOH solution boiled, then clean with deionized water rinsing, obtain the titanium plate of clean surface.
(2) preparation in two densification protection middle layer
The preparation of titania nanotube 2: using surface treated titanium plate as anode, Graphite Electrodes as negative electrode, electrolysis 4h in containing the glycerin solution of 6g/LNaF, the water content of electrolytic solution is 8g/L, constant voltage is 35V, and electrolysis temperature is 25 DEG C, and pole span is 4cm.Then by electrode clean totally at 500 DEG C of roasting 1h.
The preparation of tin-antimony oxide tight zone 3: by 9.61g citric acid and the mixing of 12.41g ethylene glycol, react 1h at 60 DEG C, then add 4.375g SnCl
45H
2o and 0.57g SbCl
3, at 90 DEG C, react 1h, prepare polybenzazole precursor liquid solution; Polybenzazole precursor liquid solution is coated in the titanium plate surface through anodic oxidation treatment, roasting 30min at 500 DEG C, this step repeats 10 times, last roasting 1h.
(3) preparation of cellular tin-antimony oxide layer 4: use (massfraction is 10%) sodium hydroxide and deionized water wash methyl methacrylate (MMA) three times respectively, gets 9gMMA and 120ml deionized water and to join in the round-bottomed flask of 500ml and to stir.Then 8gK is added
2s
2o
8under 50 ~ 90 DEG C and nitrogen atmosphere, 7h is reacted after mixing.The milky white liquid obtained is filtered, after removing aggregate, namely obtains polymethylmethacrylate (PMMA).Then the electrode for preparing is infiltrated in this liquid, then electrode is dried at 70 DEG C 24h and can obtain the gluey crystallization template of PMMA on surface.
The sodium hydroxide solution being 20% by 4g phenol and 0.7g, massfraction mixes and stirs, and adds 7g formaldehyde, transparent solution is stirred 1h at 75 DEG C.After being cooled to room temperature, use 2mol L
-1hydrochloric acid the pH of solution is adjusted to 6.Then solution is distilled, then dissolved with the ethanol of 10ml.Sodium chloride crystal unnecessary in solution is crossed and filters, filtrate and phenol-formaldehyde polymer precursor solution, use in order to next step.
The tin chloride of 2g and antimony chloride (the muriatic mol ratio of tin antimony is 12.5:1) are added ethanolic soln and stir 30min, adds 0.8g phenol-formaldehyde polymer precursor liquid and enter this solution stirred for additional 1h.Add 0.08gF127 again and stir, obtaining target liquid.To the electrode of PMMA be had to immerse above-mentioned target liquid, dry 2h at 100 DEG C after drying unnecessary solution after taking-up, this process repeats 3 times, to guarantee that target liquid is full of the space of template.Then in an ar atmosphere, 450 DEG C of roasting 2h, and then roasting 3h(temperature rise rate is 1 DEG C/min at 800 DEG C).Cellular tin-antimony oxide layer 4 can be obtained.
(4) preparation of active surface layer 5: by the coating of the manganese nitrate solution of 50w% on the intermediate layer, roasting 30min at 500 DEG C, this overshoot repeats 10 times; Then coating is containing the manganese nitrate solution of silk, and roasting 30min at 500 DEG C, this process repeats 6 times, last roasting 1h, namely obtains long-life titanium based composite anode of the present embodiment.
The application of titanium based composite anode in electrolytic manganese of the present embodiment: as a comparison, has prepared the titanium based composite anode of the manganese nitrate solution do not applied containing silk under the same conditions, and carried out electrolysis test to two kinds of electrodes, bath composition is: MnSO
4=17g/L, (NH
4)
2sO
4=110g/L, SeO
2=0.04g/L.Obtain result as shown in table 1, Comparative result can find by experiment, and the current efficiency containing the titanium based composite anode of silk is higher than the current efficiency not containing the titanium based composite anode of silk.
Table 1
Claims (10)
1. a titanium based composite anode, is characterized in that, this titanium based composite anode comprises Titanium base, two densification protection middle layer, active surface layer; Described two fine and close protection middle layer is divided into two-layer, and the first layer is titania nanotube, and the second layer is tin-antimony oxide tight zone; Described tin-antimony oxide tight zone is covered with again cellular tin-antimony oxide layer.
2. titanium based composite anode as claimed in claim 1, it is characterized in that, described Titanium base is metallic titanium plate, titanium alloy or titanium thin slice; Described active surface layer is MnO
2, IrO
2, Ta
2o
5, RuO
2in one or more mixed metal oxide.
3. a preparation method for titanium based composite anode as claimed in claim 1 or 2, is characterized in that, comprise the following steps:
(1) by Titanium base polishing, alkali cleaning or pickling, the Titanium base of clean surface is obtained;
(2) preparation in two densification protection middle layer:
The preparation of titania nanotube: using the Titanium base through above-mentioned process as anode, Graphite Electrodes, as negative electrode, carries out electrolysis, then Titanium base is carried out roasting in the alcohols electrolytic solution containing NaF, obtains the electrode containing titania nanotube;
The preparation of tin-antimony oxide tight zone: by citric acid and ethylene glycol mixing, reacting by heating, then pink salt and antimonic salt is added, reacting by heating, prepare polybenzazole precursor liquid solution, above-mentioned polybenzazole precursor liquid solution is coated in above-mentioned electrode surface, roasting, this process repeats 10 ~ 15 times, must containing the electrode of described tin-antimony oxide tight zone;
(3) cellular tin-antimony oxide layer: infiltrated in polymethylmethacrylate liquid by above-mentioned electrode, dries, and obtains the electrode that surface is covered with the gluey crystallization template of polymethylmethacrylate;
Add phenol-formaldehyde polymer precursor solution in the ethanolic soln containing pink salt and antimonic salt, after stirring, add the addition polymer of polypropylene glycol and oxyethane, stir, obtain target liquid, immersed by above-mentioned electrode in above-mentioned target liquid, roasting after drying, can obtain the electrode containing cellular tin-antimony oxide layer;
(4) preparation of active surface layer: the surface one or more in manganese, iridium, tantalum or ruthenium salts solution being coated in above-mentioned electrode, roasting, this process repeats 10 ~ 15 times; Then apply one or more in manganese, iridium, tantalum or the ruthenium salts solution containing fiber, roasting, this process repeats 4 ~ 8 times, namely obtains described titanium based composite anode.
4. preparation method as claimed in claim 3, is characterized in that, infiltrating described electrode in the temperature of polymethylmethacrylate liquid post-drying is 70 DEG C, and the time is 24h; The temperature described electrode being immersed described target liquid post-drying is 90 ~ 110 DEG C, and the time is 0.5 ~ 3h, and this process repeats 3 ~ 5 times;
After adding described citric acid and ethylene glycol in described step (2), the temperature of reacting by heating is 55 ~ 65 DEG C, and after adding described pink salt and antimonic salt, the temperature of reacting by heating is 85 ~ 95 DEG C;
The temperature of the roasting in described step (2), (4) is 450 DEG C ~ 550 DEG C, and the time is 30min ~ 180min;
In described step (3), the processing condition of roasting are: in an ar atmosphere, roasting 1 ~ 4h at 400 ~ 480 DEG C, then roasting 2 ~ 5h at 780 ~ 850 DEG C, temperature rise rate controls at 1 ~ 2 DEG C/min.
5. preparation method as claimed in claim 3, it is characterized in that, the time of described electrolysis is 1h ~ 6h, and during electrolysis, the water content control of electrolytic solution is between 1g/L ~ 10g/L, and voltage control is between 15V ~ 75V.
6. preparation method as claimed in claim 3, is characterized in that, described step (2) is SnCl with the pink salt in step (3)
45H
2o, antimonic salt is SbCl
3; Wherein in step (2), the mol ratio of citric acid, ethylene glycol, pink salt, antimonic salt is 1: 4: 0 ~ 0.5: 0 ~ 0.1.
7. the preparation method according to any one of claim 3 ~ 6, it is characterized in that, the preparation of described polymethylmethacrylate liquid comprises the following steps: with sodium hydroxide and deionized water, methyl methacrylate is washed three times respectively, then adds raw material by following weight part and parts by volume: 7 ~ 15 parts by weight of methylmethacrylate; 90 ~ 200 parts by volume deionized waters; 7 ~ 15 weight part K
2s
2o
8; Under 50 ~ 90 DEG C and nitrogen atmosphere, react 5 ~ 9h after mixing, filter, after removing aggregate, namely obtain polymethylmethacrylate liquid;
The unit ratio corresponding relation of described weight part and parts by volume is g/ml.
8. the preparation method according to any one of claim 3 ~ 6, it is characterized in that, the preparation of described phenol-formaldehyde polymer precursor solution comprises the following steps: the sodium hydroxide solution being 20% by the phenol of 3 ~ 9 weight parts and 0.2 ~ 3 weight part, massfraction mixes and stirs, 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 the pH of solution is adjusted to 5 ~ 8, then solution is distilled, then to be dissolved with ethanol, sodium chloride crystal unnecessary in solution is crossed and filters, the phenol-formaldehyde polymer precursor solution that filtrate is namely described.
9. the preparation method according to any one of claim 3 ~ 6, is characterized in that, described manganese, iridium, tantalum or ruthenium salt are respectively Mn (NO
3)
2, IrCl
3, TaCl
5, RuCl
3, described fiber comprises silk, cotton or wool.
10. the application of titanium based composite anode in electrolytic manganese, sewage disposal and chlorine industry that obtain of a titanium based composite anode as claimed in claim 1 or 2 or claim 3 ~ 9 any one preparation method.
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